Disperse dyes

ABSTRACT

A compound of the formula I ##STR1## in which D is a diazo component, 
     K is an aromatic group of formula a, b or c, ##STR2## Y is C 2-3  alkylene and the remaining symbols are as defined in the specification. These compounds are useful for dyeing or printing textile substrates based on synthetic or semisynthetic, hydrophobic, high molecular weight organic materials. Preferably, the textile substrate is made from a linear aromatic polyester, cellulose 21/2 acetate or cellulose tri-acetate. The dyeings and prints obtained show good all round fastness properties such as good thermomigration properties, lightfastness, thermofixation, blistering properties as well as good wet fastness properties, especially after thermal fixation.

According to the invention there is provided a compound of the formula I##STR3## in which D is a diazo component;

K is an aromatic group of the formula a, b or c ##STR4## where R is agroup of the formula --CH(R₄)--CO--O--R₅, --CH₂ CF₃ or --CH₂ CF₂ CF₂ H;

R₆ is hydrogen or hydroxy,

R₁ is hydrogen, chloro, C₁₋₄ alkyl, C₁₋₄ alkoxy or acylamino,

R₂ is hydrogen, C₁₋₄ alkoxy, C₁₋₄ alkoxyethoxy, chloro, bromo and

R₃ is selected from hydrogen, C₁₋₆ alkyl, C₃₋₄ alkenyl, chloroC₃₋₄alkenyl, bromoC₃₋₄ alkenyl, C₃₋₄ alkynyl, phenyl-C₁₋₄ alkyl, C₁₋₄alkoxycarbonyl-C₁₋₄ alkyl, C₃₋₄ alkenyloxycarbonyl-C₁₋₄ alkyl, C₃₋₄alkynyloxycarbonyl-C₁₋₄ alkyl, phenoxy-C₂₋₄ alkyl, --CH₂ --CH(R₈)CH₂--R₉ and C₂₋₄ alkyl substituted by 1 to 3 groups selected from halogen,cyano, C₁₋₄ alkoxy, C₁₋₄ alkylcarbonyloxy and C₁₋₄ alkoxycarbonyloxy;

or R₂ together with R₃ in the group a) form a group of theformula-*CH(CH₃)CH₂ C(CH₃)₂ where the * carbon atom is attached to thegroup a);

R₄ is hydrogen, phenyl or C₁₋₄ alkyl,

R₅ is phenyl, unsubstituted or substituted by one to three groupsselected from halogen (preferably Cl or Br) C₁₋₄ alkyl, C₁₋₄alkoxycarbonyl and C₁₋₄ alkoxy or phenyl substituted by one groupselected from formyl, cyan, rhodan, phenyl, benzyloxy, C₁₋₄alkoxycarbonyl-C₁₋₂ alkoxy, C₁₋₄ alkylcarbonylamino, C₁₋₄alkylcarbonyloxy and nitro;

or R₅ is alpha or beta naphthyl, phenyl-C₁₋₄ alkyl or1-phenyl-propenyl-3, in which the phenyl group (in phenyl C₁₋₄ alkyl and1-phenyl propenyl-3) is unsubstituted or substituted by one or twosubstituents selected from halogen, C₁₋₄ alkyl and C₁₋₄ alkoxy or by onenitro or C₁₋₄ alkoxycarbonyl group; or

R₅ is allyl, haloallyl, methallyl, propargyl, tetrahydrofuryl-2-methyl,tetrahydropyranyl-2-methyl, chlor-C₂₋₄ alkyl, bromoC₂₋₄ alkyl or a groupof the formula ##STR5## R₇ is hydrogen or C₁₋₄ alkyl; R₈ is hydroxy,C₁₋₄ alkylcarbonyloxy or C₁₋₄ alkoxycarbonyloxy;

R₉ is chloro, C₁₋₄ alkoxy, phenoxy, allyloxy or C₁₋₄ alkylcarbonyloxy;

R₁₀ is hydrogen or C₁₋₄ alkyl;

R₁₁ is hydrogen, halogen (preferably chloro or bromo), C₁₋₄ alkyl, C₁₋₄alkoxy or nitro

Y is C₂₋₃ alkylene and

n is 0 or 1;

with the proviso that when K is a group of formula b) or c), then R₃ ishydrogen.

Preferred diazo components D are single or fused carbocyclic orheterocyclic aromatic amines which may bear any of the usualsubstituents for disperse dyes, preferably excluding water solubilisinggroups, especially sulpho groups. Examples of such diazo componentscontain a phenyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl,pyrazolyl, imidazolyl, triazolyl, benzthiazolyl or benzisothiazolylgroup. The compounds of formula I are preferably monoazo compounds.

The aromatic or heteroaromatic rings can bear one to three groupsselected from the following: --COOC₁₋₈ alkyl, halogen (e.g. Cl, Br andI), nitro,cyano, rhodan, C₁₋₄ alkyl, C₁₋₄ alkoxy, phenyl and phenoxy andespecially on any thienyl or thiazolyl diazo component additionallyformyl, --CH═CH--NO₂, --CH═C(CN)₂ and --CH═C(CN)--CO--C₁₋₈ alkyl.

Preferred acyl groups include R₄₀ --Z-- in which

R₄₀ is a C₁₋₈ alkyl or phenyl group that may bear one to three groupsselected from the following: halogen (e.g. Cl, Br and I), nitro, cyano,rhodan, hydroxy, C₁₋₄ alkyl, C₁₋₄ alkoxy, phenyl, C₁₋₄ alkoxycarbonyland phenoxy groups;

Z is a radical --CO-- --O--CO--, --CO--O--, --SO₂ -- and --SO₂ --N(R₇);where * atom is attached to R₄₀ and R₇ is as defined above;

Preferred acylamino groups are --NH--Z₁ --R₄₀, where Z₁ is --CO--;##STR6## and In this Specification, any phenyl is unsubstituted orsubstituted by one or two groups selected from chloro, methyl, ethyl andC₁₋₂ alkoxy or one group nitro.

In Y preferably the alkylene group is a group of the formula --CH₂ CH₂--, --CH₂ --CH(CH₃)--, more preferably --CH₂ CH₂ --

Preferably R₄₀ is R₄₀ ' where R₄₀ ' is a C₁₋₄ alkyl group or phenyl.

Preferably D is D₁ where D₁ is a compound of formula 1 to 11 below##STR7## in which R₂₀ is hydrogen, chloro, bromo, cyano, nitro-, C₁₋₄alkoxy carbonyl, C₁₋₄ alkylsulphonyl (preferably hydrogen, cyano, chloroor nitro);

R₂₁ is chloro, bromo, nitro, C₁₋₄ alkyl, C₁₋₄ alkylsulfonyl, C₁₋₄alkylcarbonyl, aminosulfonyl, mono- or di-C₁₋₄ alkylaminosulfonyl,phenylaminosulfonyl, C₁₋₄ alkoxycarbonyl, aminocarbonyl, mono- ordi-C₁₋₄ -alkylaminocarbonyl, phenylaminocarbonyl, phenylazo,benzyloxycarbonyl, tetrahydrofurfuryl-2-oxycarbonyl, C₃₋₄alkenyloxycarbonyl oder C₃₋₄ alkinyloxycarbonyl;

R₂₂ is hydrogen, chloro, bromo or cyano;

R₂₃ is hydrogen or chloro, or when R₂₂ is hydrogen, R₂₃ is additionallyrhodan;

R₂₄ is nitro, C₁₋₄ alkylcarbonyl, C₁₋₄ alkoxycarbonyl, cyano,aminocarbonyl, mono- or di-C₁₋₂ alkylaminocarbonyl;

R₂₅ is hydrogen, chloro, bromo, C₁₋₄ alkyl or phenyl;

R₂₆ is nitro, cyano, formyl, dicyanovinyl or a group of the formula--CH═CH--NO₂, --CH═C(CN)CO--OC₁₋₄ -alkyl, H₅ C₆ --N═N-- or 3- or 4--NO₂--C₆ H₄ --N═N--;

R₂₇ is cyano or C₁₋₄ alkoxycarbonyl;

R₂₈ is C₁₋₄ alkyl or phenyl;

R₂₉ is --CN, --CH═CH₂ or phenyl;

R₃₀ is C₁₋₄ alkyl;

R₃₁ is hydrogen chlor, bromo, cyano, rhodan, nitro, C₁₋₄ alkoxycarbonylor di-C₁₋₄ alkylaminosulfonyl;

R₃₂ is hydrogen, chloro, or bromo; and

R₃₃ is C₁₋₄ alkyl, C₁₋₄ alkylcarbonyl-C₁₋₄ alkylene or --C₁₋₄alkylene-COOCH₂ CF₃

in which any phenyl group present in R₂₀ to R₃₀ is unsubstituted orsubstituted by one or two groups selected from chloro, bromo, methyl,ethyl, methoxy and ethoxy.

Preferably K is K₁ where K₁ is a group of formula a) defined above.

Preferably R is R' where R' is --CH(R₄ ')--CO--O--R₅ ' or CH₂ CF₃ whereR₄ ' and R₅ ' are defined below.

Preferably R₁ is R₁ ' where R₁ ' is selected from hydrogen, C₁₋₂ alkyl,chloro and acylamino,

Preferably R₂ is R₂ ' where R₂ ' is selected from hydrogen, chloro, C₁₋₂alkoxy, C₁₋₂ alkoxyethoxy or R₂ ' (when in formula a) together with R₃forms the group --CH(CH₃)CH₂ C(CH₃)₂.

Preferably R₃ is R₃ ' where R₃ ' is selected from hydrogen, C₁₋₄ alkyl,cyanoethyl, C₁₋₂ alkoxyethyl, C₃₋₄ alkenyl, chloroallyl, C₃₋₄ alkynyl,C₁₋₂ alkoxycarbonylmethyl, allyloxycarbonylmethyl orpropargyloxycarbonylmethyl.

Preferably R₄ is R₄ ' where R₄ ' is selected from hydrogen and C₁₋₂alkyl.

Preferably R₅ is R₅ ' where R₅ ' is phenyl, unsubstituted or substitutedby one or two substituents selected from chloro, C₁₋₂ alkyl, C₁₋₂ alkoxyand one phenyl; phenoxy ethyl; phenyl C₁₋₂ alkyl; or1-phenylpropenyl-3-, the phenyl group of each of the last threesubstituents (phenyl C₁₋₂ alkyl, phenoxy ethyl or 1-phenylpropenyl-3-)being unsubstituted or substituted by one or two groups selected fromchloro, methyl and C₁₋₂ alkoxy or one group nitro) or R₅ ' is alpha andbeta naphthyl.

Preferably Y is Y' where Y' is a group of the formula --CH₂ CH₂ -- or--CH₂ CH(CH₃)--.

More preferably R is R" where R" is is --CH(R₄ ')--CO--O--R₅ ' where R₄' is selected from hydrogen and C₁₋₂ alkyl and where R₅ ' is phenyl,unsubstituted or substituted by one or two substituents selected fromchloro, C₁₋₂ alkyl, C₁₋₂ alkoxy and one phenyl; phenyl C₁₋₂ alkyl,phenoxy ethyl or 1-phenylpropenyl-3 (the phenyl group of each of thelast three substituents phenyl C₁₋₂ alkyl, phenoxy ethyl or1-phenylpropenyl-3) being unsubstituted or substituted by one or twogroups selected from chloro, methyl and C₁₋₂ alkoxy or one group nitroor R₅ ' is alpha and beta naphthyl.

More preferably R₃ is R₃ " where R₃ " is C₁₋₄ alkyl or cyanoethyl.

More preferably R₅ is R₅ " where R₅ " is phenyl, phenoxyethyl or benzyl,in which the phenyl group of each substituent is unsubstituted orsubstituted by one or two groups selected from chloro, methyl and C₁₋₂alkoxy or one nitro group.

More preferably Y is Y" where Y" is 1,2 ethylene.

More preferably D is D₂ where D₂ is a diazo component of the2,6-dicyano-4-chlorophenyl, 2,6-dicyano-4-bromo-phenyl,2,6-dicyano-4-methylphenyl, 2,6-dicyano-4-nitrophenyl;2,4-dinitro-6-chlorophenyl, 2,4-dinitro-6-bromophenyl,2,4-dinitro-6-cyanophenyl, 2-chloro- or 2-bromo-4-nitro-6-cyanophenyl,2,4-dinitrophenyl, 2,6-dichloro- or 2,6-dibromo-4-nitrophenyl,2-chloro-4-nitro-6-bromophenyl, 2-chloro- or 2-cyano-4-nitrophenyl,2,4-dinitro-5-chlorophenyl, 2,4-dinitro-5,6-dichlorophenyl,2,5-dichloro-4-nitro-phenyl, 4-nitrophenyl, 4-phenylazophenyl, 4-C₁₋₄alkoxycarbonyl-phenyl, 2-C₁₋₄ alkoxycarbonyl-4-nitrophenyl,4-benzyloxycarbonylphenyl, 4-(tetrahydrofurfuryl-2'-oxycarbonyl)-phenyl,3,5-dicyano-4-chlorothienyl-2,3,5-dicyanothienyl-2,3-cyano-5-nitro-thienyl-2,3-acetyl-5-nitrothienyl-2,3,5-dinitrothienyl-2,3-(C₁₋₄alkoxycarbonyl)-5-nitrothienyl-2,5-phenylazo-3-cyanothienyl-2,5-phenylazo-3-cyano-4-methyl-thienyl-2,5-nitrothiazolyl-2,5-nitro-benzisothiazolyl-3,3-methyl-4-cyano-isothiazolyl-5,3-Phenyl-1,2,4-thiadiazolyl-2,5-(C₁₋₂alkylmercapto)-1,3,4-thiadiazolyl-2,3-C₁₋₄alkoxycarbonylethylmercapto-1,2,4-thiadiazolyl-5,1-cyanomethyl-4,5-dicyano-imidazolyl-2,6-nitrobenzthiazolyl-2,5-nitrobenzthiazolyl-2,6-rhodan-benzthiazolyl-2,6-chlorobenzthiazolyl-2,(5),6,(7)-dichlorobenzthiazolyl-2,or a group of the formula ##STR8## where R₃₅ is oxygen or a group of theformula ##STR9##

Most preferably R is R'" where R'" is a group of the formula --CH₂CO--O--R₅ ", where R₅ " is defined above.

Preferred compounds of formula I are of formula Ia ##STR10## in whichthe symbols D₁, R₁ ', R₂ ', R₃, Y', R₄ ' and R₅ are as defined above.

In a compound of formula Ia preferably D₁ is D₂ defined above, morepreferably D₁ is D₃ where D₃ is a diazo component of the2,4-dinitro-6-chlorophenyl, 2,4-dinitro-6-bromophenyl,2,4-dinitro-6-cyanophenyl, 2,4-dinitro-5-chlorophenyl,2,4-dinitro-5-rhodan-phenyl, or 2,4-di-nitro-5,6-dichlorophenyl series.

Most preferably D₁ is D₃ ' where D₃ ' is a diazo component of the2,4-dinitro-6-chlorophenyl or 2,4-dinitro-6-bromophenyl series.

More preferred compounds of formula I are of formula Ib ##STR11## inwhich the symbols D₂, R₁ ', R₂ ', R₃, Y', R₄ ' and R₅ are as definedabove.

Preferred compounds of formula I b are those in which R₁ ' is R₁ " andR₂ ' is R₂ ".

Alternatively preferred compounds of formula I are those of formula Ic##STR12## in which D₃ is as defined above; R' is --CH(R₄ ')--CO--O--R₅ 'or --CO--O--CH₂ CF₃ where R₄ ' and R₅ ' are defined below;

R₁ " is acylamino. (Preferably the acyl groups of acylamino are selectedfrom R₄₀ --Z-- defined above, especially NH--COC₁₋₄ alkyl);

R₂ " is C₁₋₂ alkoxy or C₁₋₂ alkoxyethoxy,

R₃ ' is selected from hydrogen, C₁₋₂ alkoxyethyl, C₃₋₄ alkenyl,chloro-C₃₋₄ alkenyl, C₃₋₄ alkynyl, C₁₋₂ alkoxy-carbonylmethyl,allyloxycarbonylmethyl or propargyl-oxycarbonylmethyl;

R₄ ' is selected from hydrogen and C₁₋₂ alkyl;

R₅ ' is phenyl, unsubstituted or substituted by one or two substituentsselected from chloro, C₁₋₂ alkyl, C₁₋₂ alkoxy and phenyl; phenyl C₁₋₂alkyl, phenoxy ethyl or 1-phenylpropenyl-3, (the phenyl group of each ofthe last three substituents (phenyl C₁₋₂ alkyl, phenoxy ethyl or1-phenylpropenyl-3) being unsubstituted or substituted by one or twogroups selected from chloro, methyl and C₁₋₂ alkoxy or one group nitro)or R₅ ' is alpha and beta naphthyl; and

is a group of the formula --CH₂ CH₂ -- or --CH₂ CH(CH₃)--.

Alternatively preferred compounds of formula Ic are those in which

D₃ is D₃ ' where D₃ ' is a diazo component of the2,4-dinitro-6-chlorophenyl or 2,4-dinitro-6bromophenyl series;

R' is R'" where R'" is a group of the formula --CH₂ CO--O--R₅ ", whereR₅ " is defined below;

R₁ " is --NH--COC₁₋₂ alkyl;

R₂ " is R₂ '" where R₂ '" is C₁₋₂ alkoxy;

R₃ ' is R_(3a) where R_(3a) is hydrogen, allyl, chloroallyl orpropargyl;

R₅ ' is R₅ " where R₅ " is phenyl, phenoxyethyl or benzyl, in which thephenyl group of each substituent is unsubstituted or substituted by oneor two groups selected from chloro, methyl and C₁₋₂ alkoxy or one groupnitro; and

Y' is Y" where Y" is 1,2 ethylene.

Further alternative preferred compounds of formula I are those offormula Id ##STR13## in which D₄ is a diazo component of the4-nitrophenyl, 2-chloro-4-nitrophenyl, 2,6-dichloro-4-nitrophenyl,2-chloro-4-nitro-6-bromophenyl or 2-cyano-4-nitrophenyl series.

R_(1a) is hydrogen, methyl, acylamino or chloro;

R_(b) is a group of the formula --CH(R₄ ')--CO--O--R₅ ', where R₄ 'where R₄ ' is selected from hydrogen and C₁₋₂ alkyl and R₅ ' is phenyl,unsubstituted or substituted by one or two substituents selected fromchloro, C₁₋₂ alkyl, C₁₋₂ alkoxy and phenyl; phenyl C₁₋₂ alkyl, phenoxyethyl or 1-phenylpropenyl-3 (the phenyl group of each of the last threesubstituents (phenyl C₁₋₂ alkyl, phenoxy ethyl or 1-phenylpropenyl-3)being unsubstituted or substituted by one or two groups selected fromchloro, methyl and C₁₋₂ alkoxy or one group nitro or R₅ ' is alpha andbeta naphthyl;

R_(3b) is C₁₋₄ alkyl, cyano-C₂₋₄ alkyl, C₁₋₄ alkoxyethyl, --C₂ H₄--O--CO--C₁₋₄ alkyl, --C₂ H₄ --O--CO--OC₁₋₄ alkyl or benzyl; and

Y is Y' where Y' is a group of the formula --CH₂ CH₂ -- or --CH₂CH(CH₃)--.

Preferred compounds of formula Id are those in which D₄ is D₅ where D₅is 2,6-dichloro-4-nitrophenyl or 2-cyano-4-nitrophenyl, R_(1a) ishydrogen, R_(3b) is C₁₋₄ alkyl, R₄ ' is hydrogen and Y' is --CH₂ CH₂ --.

The compounds of formula I can be prepared by known methods from knowncompounds. For example the compounds of formula I can be prepared bycoupling one mole of a diazotised amine of formula II

    D--NH.sub.2                                                (II)

with one mole of a compound of formula III

    H--K--N(R.sub.3)--Y--CO--OR                                (III).

Diazotisation and coupling can be carried out by known methods.

The compounds of formula II and III are known or can be made from knowncompounds by known methods.

The new compounds of formula I exhaust well from aqueous medium ontotextile material based on synthetic or semisynthetic, hydrophobic, highmolecular weight organic material. In particular the compounds offormula I are useful for dyeing or printing textile material made fromlinear aromatic polyester, cellulose 21/2 acetate and cellulosetriacetate. Linear aromatic polyester also include polyester microfibers(ref. Chemie Fasern Industrie, 43 (4) E. 34-36 (1993))

Dyeing and printing can be carried out by known methods, for example asexemplified in French Patent 1,445,371 (GB Patent 1,114,433).

The compounds of the invention have good all round fastness properties,in particular good thermomigration properties, good lightfastness, goodthermofixation, good blistering properties as well as good wet fastnessproperties, especially after thermal fixation (in particular in the M&SC4A household wash test). Worthy of mention is also the suitability ofthe compounds of formula I for Thermo-Transfer printing.

The invention will be further illustrated by the following Examples inwhich all parts and percentages are by weight.

EXAMPLE 1

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred into 100 parts of93% cold sulphuric acid and are then reacted, over 30 minutes with 32parts of 40% nitrosylsulphuric acid at 0°-5° C.

This is stirred for 3 to 4 hours at 0° to 5° C. and the resultantdiazonium solution is poured, whilst stirring well onto a mixture of35.7 parts of 3-(N-methyl-N-phenylamino)propionicacid-(2'-phenoxyethoxycarbonylmethyl ester), 100 parts of glacial aceticacid, 2 parts of amidosulphonic acid, 200 parts of water and 500 partsof ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 1a ##STR14##

This dyestuff can dye polyester material a rubin red colour and hasexcellent properties, especially good wet fastness properties afterthermofixation. This dyestuff is particularly suited for modern RapidDyeing processes.

    λmax=529 nm (DMF).

EXAMPLE 2

Example 1 is repeated using instead of 35.7 parts of3-(N-methyl-N-phenylamino)propionic acid-(2'-phenoxyethoxycarbonylmethylester), 37.1 parts of 3-(N-ethyl-N-phenylamino)propionic acid(2'-phenoxyethoxycarbonylmethyl ester). The resultant dyestuff is of theformula 2a ##STR15##

This dyestuff dyes polyester a red tone and produces good fastnessproperties, in particular good wet fastness properties afterthermofixation.

    λmax=534 nm.(DMF)

EXAMPLE 3

Example 1 is repeated using instead of 35.7 parts of3(N-methyl-N-phenylamino)propionic acid-(2'-phenoxyethoxycarbonylmethylester), 42.9 parts of 3-(N-2'-acetoxyethyl-N-phenylamino) propionic acid(2"-phenoxyethoxycarbonylmethyl ester).

The resultant dyestuff is of the formula 3a ##STR16##

This dyestuff dyes polyester a red tone and produces good fastnessproperties, in particular good wet fastness properties afterthermofixation.

    λmax=523 nm. (DMF).

EXAMPLE 4

20.7 parts of 1-amino-2,6-dichloro-4-nitrobenzene are stirred into 100parts of 93% sulphuric acid and then are reacted at 30° C. over 1 hourwith 32 parts of 40% nitrosylsulphuric acid. This mixture is stirred afurther 2 to 3 hours at this temperature and the resulting diazoniumsalt solution is added whilst slowly stirring to a mixture of 35,7 partsof 3-(N-methyl-N-phenylamino)-propionicacid-(2'-phenoxyethoxycarbonylmethyl ester), 100 parts of glacial aceticacid, 2 parts of amidosulphonic acid, 200 parts of water and 500 partsof ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 4a ##STR17##

This dyestuff can dye polyester material a yellow brown tone with goodfastness properties, in particular, good wet fastness properties afterthermal fixation.

    λ max (DMF)=439 nm.

EXAMPLE 5

21.8 parts of 2-chloro-4,6-dinitroaniline are stirred into 150 parts of93% sulphuric acid at 15°-20° C. and this is then reacted over 30minutes with 32 parts of 40% nitrosylsulphuric acid. This is stirred for2-3 hours and the resultant diazonium salt solution is slowly pouredwhilst stirring onto a mixture of 46.8 parts of3-[N-propargyl-N-(5"-acetylamino-2"-methoxy-phenylamino)]-propionicacid-(2'-phenoxyethoxycarbonylmethyl ester), 100 parts of glacial aceticacid, 2 parts of amidosulphonic acid, 200 parts of water and 500 partsof ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 5a ##STR18##

This dyestuff can dye polyester material a navy blue colour and hasexcellent fastness properties, especially fastness properties

EXAMPLE 6

21.8 parts of 2-chloro-4,6-dinitroaniline are stirred into 150 parts of93% sulphuric acid at 15°-20° C. and this is then reacted over 30minutes with 32 parts of 40% nitrosylsulphuric acid. This is stirred for2-3 hours in an ice bath and the resultant diazonium salt solution isslowly poured continuously, whilst stirring onto a mixture of 48,5 partsof 3-(N-allyl-N-(5"-acetylamino-2"-methoxyphenylamino))-propionicacid-(4'-nitro-benzyloxycarbonylmethyl ester), 100 parts of glacialacetic acid, 2 parts of amidosulphonic acid and 300 parts of ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 6a ##STR19##

This dyestuff can dye polyester material a navy blue colour and hasexcellent fastness properties, especially wet fastness properties afterthermofixation.

    λ max (DMF)=597 nm.

EXAMPLE 7

21.8 parts of 2-chloro-4,6-dinitroaniline are stirred into 150 parts of93% sulphuric acid at 15°-20° C. and this is then reacted over 30minutes with 32 parts of 40% nitrosylsulphuric acid. This is stirred for2-3 hours in an ice bath and the resultant diazonium salt solution isslowly poured continuously, whilst stirring onto a mixture of 40 partsof 3-N-(5"-acetylamino-2"-methoxyphenylamino)-propionicacid-(benzyloxycarbonylmethyl ester), 100 parts of glacial acetic acid,and 300 parts of ice/water.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C.

The resulting dyestuff is of the formula 7a ##STR20##

This dyestuff can dye polyester material and polyester/cotton mixedfabrics a navy blue colour and has excellent fastness properties,especially wet fastness properties after thermofixation.

    λ max (DMF)=595 nm.

EXAMPLE 8

21.8 parts of 2-chloro-4,6-dinitroaniline are stirred into 150 parts of93% sulphuric acid at 15°-20° C. and this is then reacted over 30minutes with 32 parts of 40% nitrosylsulphuric acid. This is stirred for2-3 hours in an ice bath and the resultant diazonium salt solution isslowly poured continuously, whilst stirring onto a mixture of 44.5 partsof 3-[N-allyl-N-(5"-acetylamino-2"-methoxyphenylamino)]-propionicacid-(2'-methyl-phenoxycarbonylmethyl)-ester, 100 parts of glacialacetic acid, 2 parts of amidosulphonic acid and 300 parts of ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 8a ##STR21##

This dyestuff can dye polyester fibre material a navy blue colour andhas excellent fastness properties, especially good wet fastnessproperties after thermofixation.

    λ max (DMF)=597 nm.

The compound of formula 8a is particularly suitable for use alone or ina navy blue or black mixture and is particularly suitable for use inrapid dyeing, especially the Foron (registered trademark) RD process.

EXAMPLE 9

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred into 150 parts of93% sulphuric acid at 15°-0° C. and this is then reacted over 30 minutesat 0 to 5 with 32 parts of 40% nitrosylsulphuric acid. This is stirredfor 2-3 hours in an ice bath and the resultant diazonium salt solutionis slowly poured continuously, whilst stirring onto a mixture of 34.2parts of 3-(N-methyl-N-phenylamino)-propionicacid-3',5'-dimethylphenoxycarbonylmethyl ester, 100 parts of glacialacetic acid, 2 parts of amidosulphonic acid and 500 parts of ice/water.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 9a ##STR22##

This dyestuff can dye polyester fibre material a rubin colour and hasexcellent fastness properties

    λ max (DMF)=532 nm.

The compound of formula 9a is particularly suitable for use alone or inmixture and is particularly suitable for use in rapid dyeing, especiallythe Foron (registered trademark) RD process. The wet fastness propertiesare good.

EXAMPLE 10

18.6 parts of 2-amino-4-chloro-3-cyano-5-formyl-thiophene are dissolvedin 200 parts of 85% sulphuric acid. Whilst stirring, 33 parts of 40%nitrosyl sulphuric acid are added and stirred for about 3 hours at about0° C. The resulting brown diazonium salt solution is added whilststirring well, to a solution of 18 parts of3-(N-ethyl-N-3"-methylphenylamino)-propionic acid-2'- and 4')respectively) methylphenoxycarbonylmethyl ester and 2 parts ofamidosulphonic acid in 50 parts of 5% sulphuric acid. The couplingtemperature is maintained by external cooling any by the addition of 200parts of ice. The dyestuff suspension is stirred for 1 to 2 hours,filtered and washed acid free with 300 parts of water. The product isdried under vacuum at 50° C. An isomeric dyestuff mixture of the formula10a ##STR23## results.

This mixture dyes polyester a brilliant reddish blue tone with goodfastness properties. The λ max. (DMF)=610 nm

EXAMPLE 11

21.8 parts of 2-chloro-4,6-dinitroaniline are stirred into 150 parts of93% sulphuric acid at 15°-20° C. and then this is reacted at 30° C. over1 hour with 32 parts of 40% nitrosylsulphuric acid. This mixture isstirred a further 2 to 3 hours at this temperature and the resultingdiazonium salt solution is added whilst slowly stirring to a mixture of44.5 parts of 3-(N-(5"-acetylamino-2"-methoxyphenylamino))-propionicacid-n-(4-nitro-benzyloxy-carbonylmethyl ester), 100 parts of glacialacetic acid, 2 parts of amidosulphonic acid and 300 parts of ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 11a ##STR24##

This dyestuff can dye polyester fibre material a navy blue colour andhas excellent fastness properties, especially good wet fastnessproperties after thermofixation.

    λ max (DMF)=595 nm.

The compound of formula 11a is particularly suitable for use alone or ina navy blue or black mixture and is particularly suitable for use inrapid dyeing, especially the Foron (registered trademark) RD process.

EXAMPLE 12

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred into 100 parts of93% cold sulphuric acid and are then reacted, over 30 minutes with 32parts of 40% nitrosylsulphuric acid at 0°-5° C.

This is stirred for 3 to 4 hours at 0° to 5° C. and the resultantdiazonium solution is poured, whilst stirring well onto a mixture of40.1 parts of 3-(N-methyl-N-phenylamino)propionicacid-(2"-phenoxyethoxy-2'-ethoxy-carbonylmethyl ester), 100 parts ofglacial acetic acid, 2 parts of amidosulphonic acid, 200 parts of waterand 500 parts of ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is of theformula 12a ##STR25##

This dyestuff can dye polyester material a rubin red colour and hasexcellent fastness properties, especially good wet fastness propertiesafter thermofixation. This dyestuff is particularly suited for modernRapid Dyeing processes.

    λmax=531 nm (DMF).

EXAMPLES 13-433

The compounds of Tables 1 to 17 can be synthesised from known productsanalogously to an appropriate method according to Example 1-12.

                                      TABLE 1                                     __________________________________________________________________________     ##STR26##                                                                    Ex.                                                 Nuance                    No.                                                                              R.sub.6                                                                         R.sub.7                                                                              R.sub.2                                                                            R.sub.1     R.sub.3     R.sub.5    on PES                    __________________________________________________________________________    13 Cl                                                                              NO.sub.2                                                                             OCH.sub.3                                                                          NHCOCH.sub.3                                                                              CH.sub.2 CHCHCl                                                                           C.sub.6 H.sub.4 -2-CH.sub.3                                                              blue                      14 Cl                                                                              "      OC.sub.2 H.sub.5                                                                   "           CH.sub.2 CHCH.sub.2                                                                       "          "                         15 Cl                                                                              "      "    "           CH.sub.3    C.sub.6 H.sub.4 -2-COOC.sub.2                                                 H.sub.5    "                         16 Br                                                                              "      OCH.sub.3                                                                          NHCOCH.sub.3                                                                              CH.sub.2 CHCH.sub.2                                                                       C.sub.6 H.sub.4 -2-COOCH.sub.3                                                           "                         17 Cl                                                                              "      "    "           H            C.sub.6 H.sub.3 -2-CH.sub.3                                                  -4-Cl      "                         18 Cl                                                                              "      "    "           C.sub.2 H.sub.4 COOCH.sub.3                                                               C.sub.6 H.sub.4 -4-COOCH.sub.3                                                           "                         19 Cl                                                                              "      "    "           CH.sub.2 COOC.sub.2 H.sub.5                                                               C.sub.6 H.sub.4 -4-CH.sub.3                                                              "                         20 Cl                                                                              "      "    "           CH.sub.2 CHCH.sub.2                                                                       C.sub.6 H.sub.4 -2-CH(CH.sub.3).s                                             ub.2       "                         21 Cl                                                                              "      "    "                                                            n-C.sub.4 H.sub.9                                                                C.sub.6 H.sub.4 -2-CH.sub.3                                                     "                                                                        22 Cl                                                                              "      "    "           CH.sub.2 CH(CH.sub.3)CH.sub.2                                                             C.sub.6 H.sub.5                                                                          "                         23 Cl                                                                              "      "    "           CH.sub.2 CHCHCl                                                                           C.sub.6 H.sub.4 -2-C.sub.2                                                    H.sub.5    "                         24 Cl                                                                              "      "    NHCOCH.sub.2 OCH.sub.3                                                                    "           C.sub.6 H.sub.3 -2,6-(CH.sub.3).s                                             ub.2       "                         25 Cl                                                                              "      "    NHCOCH.sub.2 OH                                                                           CH.sub.2 C.sub.6 H.sub.5                                                                  C.sub.6 H.sub.4 -2-CH(CH.sub.3).s                                             ub.2       "                         26 Cl                                                                              "      "    NHCOCH.sub.2 OCOCH.sub.3                                                                  CH.sub.2 CHCH.sub.2                                                                       (CH.sub.2).sub.3 Cl                                                                      "                         27 Cl                                                                              "      "    CH.sub.3    H           C.sub.6 H.sub.3 -2,6-(CH.sub.3).s                                             ub.2       violet                    28 Br                                                                              "      "    "           H           "          "                         29 Cl                                                                              "      "    NHCOCH.sub.3                                                                              CH.sub.2 CHOHCH.sub.2 Cl                                                                  C.sub.6 H.sub.4 -2-CH.sub.3                                                              blue                      30 Cl                                                                              "      "    "           CH.sub.2 CH(OAc)OAc                                                                       C.sub.6 H.sub.4 -2-OCH.sub.3                                                             "                         31 Br                                                                              "      "    "           H           C.sub.6 H.sub.4 -2-Allyl                                                                 "                         32 Br                                                                              "      "    "           C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                         33 I "      "    "           "           "          "                         34 Cl                                                                              "      "    "           C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.6 H.sub.4 -2-CH(CH.sub.3).s                                             ub.2       "                         35 Cl                                                                              "      "    "           H           C.sub.6 H.sub.4 -4-COOC.sub.4                                                 H.sub.9    "                         36 Cl                                                                              "      "    "           (CH.sub.2).sub.4 OCOCH.sub.3                                                              C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                         37 Cl                                                                              "      "    "           CH.sub.2 CH(OAc)CH.sub.3                                                                  "          "                         38 Cl                                                                              "      "    "           (CH.sub.2).sub.3 2C.sub.6 H.sub.4 -2-C.sub.2                                  H.sub.5     "                                    39 Cl                                                                              "      OC.sub.2 H.sub.5                                                                   NHCOCH.sub.3                                                                              H           CH.sub.2 CH.sub.2 Cl                                                                     "                         40 Cl                                                                              "      OCH.sub.3                                                                          NHCOOC.sub.2 H.sub.5                                                                      H           (CH.sub.2).sub.3 Cl                                                                      "                         41 Cl                                                                              "      "    NHCOOCH.sub.3                                                                             H           (CH.sub.2).sub.4 Br                                                                      "                         42 Cl                                                                              "      "    "           H           (CH.sub.2).sub.4 Cl                                                                      "                         43 Cl                                                                              "      "    "           H           (CH.sub.2).sub.3 C.sub.6                                                                 ".sub.5                   44 Cl                                                                              "      "    NHCOH       H           CH.sub.2 C.sub.6 H.sub.5                                                                 "                         45 Cl                                                                              "      "    NHCOCHCH.sub.2                                                                            H           "          "                         46 Cl                                                                              "      "    "           H           CH.sub.2 CH.sub.2 Cl                                                                     "                         47 H Cl     H    NHCOCH.sub.3                                                                              CH.sub.2 CHCH.sub.2                                                                       C.sub.6 H.sub.3 -2,6-(CH.sub.3).s                                             ub.2       rubin                     48 H CN     H    H           "           "          "                         49 H "      H    H           C.sub.2 H.sub.5                                                                           C.sub.6 H.sub.4 -2-COCH.sub.3                                                            "                         50 H "      H    H           CH.sub.3    C.sub.6 H.sub.4 -2-COC.sub.2                                                  H.sub.5    "                         51 H "      H    H           CH.sub.2 CHCHCl                                                                           C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                         52 H Cl     H    NHCOCH.sub.3                                                                              CH.sub.2 CHCH.sub.2                                                                       C.sub.6 H.sub.4 -2-C.sub.2                                                    H.sub.5    red                       53 H "      H    "                                                            n-C.sub.4 H.sub.9                                                                C.sub.6 H.sub.4 -2-COOCH.sub.3                                                  "                                                                        54 H COOCH.sub.3                                                                          H    H           CH.sub.3    "          scarlet                   55 H H      H    NHCOCH.sub.3                                                                              "           C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                         56 Cl                                                                              Cl     H    H           "           "          yellow                                                                        brown                     57 " "      H    H           "           C.sub.6 H.sub.4 -3-CH.sub.3                                                              "                         __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR27##                                                                                                                   Nuance                         Example                                                                            R.sub.2 R.sub.1     R.sub.3   R.sub.5     on PES                         __________________________________________________________________________    DK = 4-chloro-5-formyl-thiazolyl-2-                                           58   OCH.sub.3                                                                             NHCOCH.sub.2 OC.sub.2 H.sub.5                                                             H         C.sub.6 H.sub.3 -2,4-(CH.sub.3).sub.2                                                     blue                           59   "       NHCOCH.sub.3                                                                              CH.sub.2 CHCH.sub.2                                                                     C.sub.6 H.sub.4 -2-CH.sub.3                                                               "                              60   "       CH.sub.3    H         "           violet                         61   H       NHCOCH.sub.3                                                                              C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.4 -2-CH(CH.sub.3).sub.2                                                     "                              62   H       H           "         C.sub.6 H.sub.4 -2-CH.sub.3                                                               violet                         63   H       H           "         C.sub.6 H.sub.3 -2-COOC.sub.2 H.sub.5                                                     "                              64   H       H           CH.sub.3  C.sub.6 H.sub.4 -2-COC.sub.2 H.sub.5                                                      rubin                          65   H        OH         CH.sub.2 CHCH.sub.2                                                                     C.sub.6 H.sub.4 -4-CH.sub.3                                                               "                              DK = 4-Chlor-5-cyano-thiazolyl-2-                                             66   H       H           C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.3 -2,4-(CH.sub.3).sub.2                                                     violet                         67   H       NHCOCH.sub.3                                                                              "         C.sub.6 H.sub.4 -2-CH.sub.3                                                               blue                           68   OCH.sub.3                                                                             "           H         C.sub.6 H.sub.4 -2-COOCH.sub.3                                                            "                              69   "       "           H         "           green                          70   H       CH.sub.3    C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.4 -2-C.sub.2 H.sub.5                                                        blue                           DK = 5-Nitro-thiazolyl-2-                                                     71   OCH.sub.3                                                                             NHCOCH.sub.3                                                                              H         C.sub.6 H.sub.3 -2,6-(CH.sub.3)                                                           blue                           72   H       "           C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.4 -2-OCH.sub.3                                                              "                              73   H       CH.sub.3    "         C.sub.6 H.sub.4 -2-CH.sub.3                                                               violet                         DK = 4-Cyano-3-methyl-isothiazolyl-5-                                         74   H       H           CH.sub.3  C.sub.6 H.sub.4 -2-CH.sub.3                                                               red                            75   H       H           C.sub.2 H.sub.4 OCH.sub.3                                                               C.sub.6 H.sub.3 -2,4-(CH.sub.3).sub.2                                                     "                              76   H       NHCOCH.sub.3                                                                              CH.sub.2 CCH.sub.2                                                                      C.sub.6 H.sub.3 -2,3-(CH.sub.3).sub.2                                                     "                              DK = 3-Phenyl-1,2,4-thiadiazolyl-5-                                           77   H       H           C.sub.2 H.sub.5                                                                         CH.sub.2 CH.sub.2 Br                                                                      red                            78   H       CH.sub.3    CH.sub.2 CHCHCH.sub.3                                                                   C.sub.6 H.sub.4 -2-CH.sub.3                                                               "                              __________________________________________________________________________                                                   Nuance                         Ex. No.                                                                            R.sub.50                                                                             R.sub.2                                                                            R.sub.1   R.sub.3  R.sub.5    on PES                         __________________________________________________________________________    DK = 5-R.sub.50 mercapto-1,3,4-thiadiazolyl-2-                                79   5-C.sub.2 H.sub.5                                                                    H    NHCOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.3 -2,4-(CH.sub.3).sub.2                                                    red                            80   5-CH.sub.2 C.sub.6 H.sub.5                                                           H    "         "        CH.sub.2 C.sub.6 H.sub.5                                                                 "                              DK = Benzthiazolyl-2-substituted by R.sub.50                                  81   (5),6,(7)Cl                                                                          H    CH.sub.3  CH.sub.3 C.sub.6 H.sub.4 -2-CH(CH.sub.3).sub.2                                                    red                            82   6-NO.sub.2                                                                           H    "         C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                              DK = 5-Nitro-2,1-Benzisothiazolyl-3-                                          83          H    NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                              CH.sub.2 CH.sub.2 Cl                                                                     green blue                     84          H    H         C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-CH.sub.3                                                              blue                           DK = 4-Chloro-3-cyano-5-formyl-thienyl-2-                                     85          OCH.sub.3                                                                          NHCOCH.sub.3                                                                            H        C.sub.6 H.sub.3 -2,4-(CH.sub.3).sub.2                                                    green blue                     86          "    NHCOCH.sub.2 OCH.sub.3                                                                  H        "          "                              87          "    NHCOCH.sub.3                                                                            CH.sub.2 CHCH.sub.2                                                                    C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                              88          H    "         C.sub.2 H.sub.5                                                                        "          blue                           89          H    NHCOCH.sub.2 OCH.sub.3                                                                  "        "          "                              90          OCH.sub.3                                                                          CH.sub.3  H        "          "                              91          H    "         C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-CH(CH.sub.3).sub.2                                                    red blue                       DK = 4-(substituierte)-3,5-dicyano-thienyl-2-                                 92   4-Cl   H    CH.sub.3  C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-CH.sub.3                                                              red blue                       93   "      H    NHCOCHCH.sub.2                                                                          "        "          blue                           94   "      OC.sub.2 H.sub.5                                                                   NHCOC.sub.2 H.sub.4 Cl                                                                  H        C.sub.6 H.sub.4 -4-COOCH.sub.3                                                           blue                           95   "      H    CH.sub.3  C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.3 -2,4-(CH.sub.3).sub.2                                                    red blue                       96   4-CH.sub.3                                                                           H    "         "        C.sub.6 H.sub.3 -4-Cl-3-CH.sub.3                                                         violet                         97   "      H    H         "        C.sub.6 H.sub.4 -2-Allyl                                                                 rubin                          DK = 3-Cyano-5-nitro-thienyl-2-                                               98          H    CH.sub.3  C.sub.2 H.sub.5                                                                        CH.sub.2).sub.3 Cl                                                                       blue                           99          H    "         "        C.sub.6 H.sub.3 -2,6-(CH.sub.3).sub.2                                                    "                              100         H    NHCOCH.sub.3                                                                            "        CH.sub.2 C.sub.6 H.sub.5                                                                 "                              DK = 3,5-Dinitro-thienyl-2-                                                   101         H    NHCOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-CH.sub.3                                                              green                          102         H    CH.sub.3  "        C.sub.6 H.sub.4 -2-CH.sub.3                                                              blue                           103         H    H         "        C.sub.6 H.sub.4 -2-COOC.sub.2                                                            ".sub.5                        DK = 3-Acetyl-5-nitro-thienyl-2-                                              104         H    CH.sub.3  C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.3 -2,6-(CH.sub.3).sub.2                                                    blue                           105         H    "                                                            n-C.sub.4 H.sub.9                                                                  CH.sub.2 C.sub.6 H.sub.5                                                             "                                                                 DK = 3-Alkoxycarbonyl-5-nitro-thienyl-2-                                      106         H    CH.sub.3  C.sub.2 H.sub.5                                                                        CH.sub.2 CH.sub.2 CHClCH.sub.3                                                           red blue                       107         H    "         "        C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                              DK = 3-Cyano-5-(substituted)phenylazo-thienyl-2-                              108  (4'-H) H    H         C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-CH.sub.3                                                              red blue                       109  "      H    H         C.sub.2 H.sub.4 0COCH.sub.3                                                            C.sub.6 H.sub.4 -2-CH(CH.sub.3).sub.2                                                    "                              PYRAZOLE/IMIDAZOLE/TRIAZOLE:                                                  DK = 4-Cyano-3-methyl-1-phenyl-pyrazolyl-5-                                   110         H    NHCOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-CH.sub.3                                                              red                            111         H    CH.sub.3  C.sub.2 H.sub.4 0CH.sub.3                                                              C.sub.6 H.sub.4 -2-COOCH.sub.3                                                           scarlet.                       DK = 1-Cyanomethyl-4,5-dicyano-imidazolyl-2-                                  112         H    CH.sub.3                                                     n-C.sub.6 H.sub.13                  C.sub.6 H.sub.4 -2-CH.sub.3                                                              red                            113         H    "         C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.3 -2,4-(CH.sub.3).sub.2                                                    "                              DK = 4-Cyano-1(substituted R.sub.50)1,2,3-triazolyl-5-                        114  (1-Allyl)                                                                            H    NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                              C.sub.6 H.sub.4 -2-CH.sub.3                                                              red                            115  (1-Benzyl)                                                                           H    NHCOCH.sub.2 OCH.sub.3                                                                  CH.sub.2 CHCH.sub.2                                                                    CH.sub.2 CH.sub.2  Cl                                                                    "                              __________________________________________________________________________

The dyestuffs of the following formula ##STR28## in which the symbolsare defined in Table 3 can be made from known compounds by anappropriate method of Examples 1 to 12.

                                      TABLE 3                                     __________________________________________________________________________                                            Nuance                                Ex. No.                                                                            R.sub.2                                                                            R.sub.1   R.sub.3  R.sub.5    on PES                                __________________________________________________________________________    DK = 2,4-Dinitro-5-rhodano-phenyl-1-                                          116  OC.sub.2 H.sub.5                                                                   NHCOCH.sub.2 OCH.sub.3                                                                  H        CH.sub.2 CH.sub.2 Cl                                                                     green blue                            117  OCH.sub.3                                                                          CH.sub.3  H        C.sub.6 H.sub.4 -2-CH.sub.3                                                              blue                                  118  H    NHCOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4 -2-OCH.sub.3                                                             "                                     119  H    CH.sub.3  "        "          "                                     120  H    H         "        C.sub.6 H.sub.4 -4-COOC.sub.2 H.sub.5                                                    red blue                              DK = 2,4-Dinitro-5-chloro-phenyl-1-                                           121  OCH.sub.3                                                                          NHCOCH.sub.3                                                                            H        C.sub.6 H.sub.4 -2-CH(CH.sub.3).sub.2                                                    blue                                  122  "    NHCOC.sub.2 H.sub.5                                                                     H        C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                                     123  "    NHCOOCH.sub.3                                                                           CH.sub.2 CHCH.sub.2                                                                    C.sub.6 H.sub.4 -4-CH.sub.3                                                              "                                     DK = 2,4-Dinitro-5,6-dichloro-phenyl-1-                                       124  "    NHCOCH.sub.3                                                                            (CH.sub.2).sub.3 CN                                                                    CH.sub.2 CH.sub.2 Cl                                                                     blue                                  125  "    "         H        C.sub.6 H.sub.4 -4-COOCH.sub.3                                                           "                                     DK = 2,6-Dicyano-4-methyl-phenyl-1-                                           126  H    NHSO.sub.2 CH.sub.3                                                                     C.sub.2 H.sub.5                                                                        (CH.sub.2).sub.3 Cl                                                                      red                                   127  H    "         "        C.sub.6 H.sub.4 -2-CH.sub.3                                                              "                                     128  H    CH.sub.3  "        "          "                                     DK = 2,6-Dicyano-4-bromo-phenyl-1-                                            129  H    OH        CH.sub.2 CHCH.sub.2                                                                    C.sub.6 H.sub.3 -2-CH.sub.3                                                              red                                   130  H    "         C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.3 -2,4-(CH.sub.3).sub.2                                                    "                                     __________________________________________________________________________

Compounds of the formula ##STR29## in which the symbols are defined inTable 4 can be prepared from known compounds by an appropriate method ofExample 1 to 12.

                  TABLE 4                                                         ______________________________________                                        Ex.                                     Nuance                                No.  R.sub.6 R.sub.7                                                                             R.sub.3        R.sub.4                                                                             on PES                                ______________________________________                                        131  --CN    H     --C.sub.2 H.sub.5                                                                            H     Rubine                                132  Cl      Cl    --CH.sub.3     H     yellow                                                                        brown                                 133  --CN    H     --CH.sub.2 CH.sub.2 O--CO--OCH.sub.3                                                         H     Red                                   134  "       H     --CH.sub.2 CH.sub.2 O--COCH.sub.3                                                            H     "                                     135  Cl      Cl    --CH.sub.3     --CH.sub.3                                                                          yellow                                                                        brown                                 ______________________________________                                    

Compounds of the formula ##STR30## in which the symbols are defined inTable 5 can be prepared from known compounds by an appropriate method ofExample 1 to 12.

                                      TABLE 5                                     __________________________________________________________________________                                    Nuance                                        Ex. No.                                                                            R.sub.7                                                                         R.sub.6                                                                           R.sub.2                                                                            R.sub.1                                                                              R.sub.3                                                                           R.sub.5                                                                            on PES                                        __________________________________________________________________________    136  Cl                                                                              --NO.sub.2                                                                        --OCH.sub.3                                                                        --NHCOCH.sub.3                                                                       H   --CH.sub.3                                                                         blue                                          137  Cl                                                                              "   "    "      H   --C.sub.2 H.sub.5                                                                  "                                             138  Cl                                                                              "   "    "      H   --C.sub.4 H.sub.9 -n                                                               "                                             139  H --CN                                                                              H    H      --CH.sub.3                                                                        --C.sub.2 H.sub.5                                                                  rubin                                         140  Cl                                                                              Cl  H    H      "   "    yellow brown                                  __________________________________________________________________________

Compounds of the formula ##STR31## in which the symbols are defined inTable 6 can be prepared from known compounds by an appropriate method ofExample 1 to 12.

                                      TABLE 6                                     __________________________________________________________________________    Ex. No                                                                             R.sub.6                                                                           R.sub.7                                                                          R.sub.1 R.sub.2                                                                            R.sub.3   R.sub.x                                                                           Nuance on PES                          __________________________________________________________________________    141  --NO.sub.2                                                                        Br --NHCOCH.sub.3                                                                        H    --C.sub.2 H.sub.5                                                                       H   violet                                 142  "   Cl "       H    --C.sub.4 H.sub.9                                                                       H   "                                      143  "   "  "       H    --(CH.sub.2).sub.4 OCOCH.sub.3                                                          H   "                                      144  "   "  --CH.sub.3                                                                            OCH.sub.3                                                                          --CH.sub.3                                                                              H   "                                      145  "   "  "       "    --C.sub.2 H.sub.4 OCOCH.sub.3                                                           H   "                                      146  "   "  "       "    H         H   "                                      147  "   "  "       "    H         4-NO.sub.2                                                                        "                                      148  "   Br "       "    H         H   "                                      149  "   H  --NHCOCH.sub.3                                                                        H    --CH.sub.2 CH═CH--Cl                                                                H   ruby red                               150  "   H  "       H    --CH.sub.2 CH═CH.sub.2                                                              H   "                                      151  "   H  H       H    -- CH.sub.3                                                                             H   "                                      152  --CN                                                                              H  H       H    --C.sub.2 H.sub.5                                                                       H   "                                      153  "   H  H       H    --CH.sub.2 CH═CH.sub.2                                                              H   "                                      154  --CN                                                                              H  H       H    --CH.sub.3                                                                              H   ruby red                               155  "   H  --NHCOCH.sub.3                                                                        H    --CH.sub.2 CH═CH.sub.2                                                              H   "                                      156  "   H  --NHCOC.sub.2 H.sub.5                                                                 H    --C.sub.2 H.sub.4 OCH.sub.3                                                             H   "                                      157  Cl  H  --NHCOCH.sub.3                                                                        H    --C.sub.2 H.sub.5                                                                       H   red                                    158  H   H  H       H    --C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                    H   scarlet                                159  Cl  Cl H       H    --CH.sub.3                                                                              H   yellow brown                           160  "   "  H       H    --C.sub.2 H.sub.5                                                                       H   "                                      161  --NO.sub.2                                                                        Cl --NHCOCH.sub.3                                                                        --OCH.sub.3                                                                        --CH.sub.2 C.tbd.CH                                                                     H   navy blue                              162  "   "  "       "    "         4-NO.sub.2                                                                        "                                      163  "   Br "       "    H         "   "                                      164  "   "  --NHCOOCH.sub.3                                                                       --OC.sub.2 H.sub.5                                                                 H         H   "                                      165  "   "  "       --OCH.sub.3                                                                        H         4-NO.sub.2                                                                        "                                      166  "   "  "       "    --CH.sub.2 C.tbd.CH                                                                     "   "                                      167  "   Cl --NHCOCH.sub.3                                                                        "    --CH.sub.2 COOCH.sub.3                                                                  H   "                                      168  "   "  "       "    --CH.sub.2 COOCH.sub.2 C.tbd.CH                                                         H   "                                      169  "   "  --NHCOC.sub.2 H.sub.5                                                                 "    H         H   "                                      170  "   "  --NHCOOCH.sub.3                                                                       "    H         H   "                                      171  "   "  --NHCOOCH.sub.3                                                                       "    H         4-Cl                                                                              "                                      172  "   "  --NHCOCH═CH.sub.2                                                                 "    H         H   "                                      173  "   "  --NHCOCH.sub.3                                                                        "    --CH.sub.2 CH═CH--Cl                                                                H   "                                      174  "   "  "       --OC.sub.2 H.sub.5                                                                 --C.sub.2 H.sub.4 COOCH.sub.3                                                           H   "                                      175  "   "  "       "    --(CH.sub.2).sub.3 CN                                                                   H   "                                      176  "   "  "       --OCH.sub.3                                                                        --C.sub.2 H.sub.4 OCOCH.sub.3                                                           H   "                                      177  "   "  "       "    --C.sub.2 H.sub.4 COOCH.sub.2 C.tbd.CH                                                  H   "                                      178  "   "  "       "    --CH.sub.2 COOC.sub.6 H.sub.5                                                           H   "                                      179  "   "  "       "    --C.sub.2 H.sub.4 OCH.sub.3                                                             4-CH.sub.3                                                                        "                                      180  "   "  "       --OC.sub.2 H.sub.5                                                                 --CH.sub.2 C═CH                                                                     4-NO.sub.2                                                                        "                                      __________________________________________________________________________

Compounds of the formula ##STR32## in which the symbols are defined inTable 7 can be prepared from known compounds by an appropriate method ofExample 1 to 12.

                                      TABLE 7                                     __________________________________________________________________________                                                    Nuance                        Ex. No.                                                                            R.sub.8                                                                         R.sub.6                                                                           R.sub.7                                                                         R.sub.1 R.sub.2                                                                            R.sub.3     Z         on PES                        __________________________________________________________________________    181  H NO.sub.2                                                                          Cl                                                                              NHCOCH.sub.3                                                                          OCH.sub.3                                                                          H                                                                                          ##STR33##                                                                              navy blue                     182  H "   Br                                                                              "       "    H           "         "                             183  H "   Cl                                                                              "       "    CH.sub.2 CCH                                                                              "         "                             184  H "   " "       OC.sub.2 H.sub.5                                                                   CH.sub.2 COOCH.sub.3                                                                      "         "                             185  H "   " NHCOC.sub.2 H.sub.5                                                                   OCH.sub.3                                                                          H           "         "                             186  H "   " CH.sub.3                                                                              "    H           "         violet                        187  H CN  H H       H    C.sub.2 H.sub.5                                                                           "         ruby red                      188  H "   H H       H    CH.sub.2 CHCH.sub.2                                                                       "         "                             189  H Cl  Cl                                                                              H       H    CH.sub.3    "         yellow                                                                        brown                         190  H "   " H       H    C.sub.2 H.sub.5                                                                           "         yellow                                                                        brown                         191  H NO.sub.2                                                                          " NHCOCH.sub.3                                                                          OCH.sub.3                                                                          H           C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                         navy blue                     192  H "   Br                                                                              "       "    H           "         "                             193  H "   Cl                                                                              "       "    CH.sub.2 CCH                                                                              "         "                             194  H "   " "       "    CH.sub.2 CHOHCH.sub.2 Cl                                                                  "         "                             195  H "   " NHCOCH.sub.3                                                                          "    H           (CH.sub.2).sub.3 C.sub.6 H.sub.5                                                        "                             196  H "   " NHCHO   "    H           "         "                             197  H "   Br                                                                              NHCOCH.sub.3                                                                          "    H           "         "                             198  Cl                                                                              "   Cl                                                                              "       "    H           CH.sub.2 C.sub.6 H.sub.5                                                                "                             199  Cl                                                                              "   " "       "    CH.sub.2 CCH                                                                              "         "                             200  Cl                                                                              "   " H       "    CH.sub.2 CHCH.sub.2                                                                       "         "                             __________________________________________________________________________

Compounds of the formula ##STR34## in which the symbols are defined inTable 8 can be prepared from known compounds by an appropriate method ofExample 1 to 10.

    __________________________________________________________________________                                                  Nuance                          Ex. No.                                                                            R.sub.30     Z     R.sub.1                                                                              R.sub.2                                                                            R.sub.3   on PES                          __________________________________________________________________________    201  O            CCN   CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                         blue                            202  O            "     "      H    C.sub.4 H.sub.9                                                                         "                               203  CHNO.sub.2   "     "      H    C.sub.2 H.sub.5                                                                         green blue                      204  C(CN)COOC.sub.2 H.sub.5                                                                    "     "      H    "         "                                    C(CN)COOC.sub.4 H.sub.9 (n)                                                   (1:1 ratio)                                                              205  O            "     NHCOCH.sub.3                                                                         H    "         blue                            206  O            N     CH.sub.3                                                                             H    "         violet                          207  O            "     NHCOCH.sub.3                                                                         OCH.sub.3                                                                          H         navy blue                       208  O            "     "      "    CH.sub.2 CHCH.sub.2                                                                     "                               209  O            "     "      "    CH.sub.2 CHCHCl                                                                         "                               210  O            "     "      OC.sub.2 H.sub.5                                                                   H         "                               211  O            "     "      "    CH.sub.2 CHCH.sub.2                                                                     "                               212  O            "     "      "    CH.sub.2 CCH                                                                            "                               213  O.sub.2 NCH  "     CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                         blue                            214                                                                                 ##STR35##   "     "      H    "         "                               215                                                                                 ##STR36##   "     "      OCH.sub.3                                                                          H         green blue                      __________________________________________________________________________

Compounds of the formula ##STR37##

in which the symbols are defined in Table 9 can be prepared from knowncompounds by an appropriate method of Example 1 to 12.

                                      TABLE 9                                     __________________________________________________________________________    Ex. No.                                                                            DK             R.sub.1 R.sub.2                                                                            Y       R.sub.3                                                                            Nuance on                       __________________________________________________________________________                                                  PES                             216                                                                                 ##STR38##     H       H    C.sub.3 H.sub.6                                                                       CH.sub.3                                                                           rubin                           217  "              H       H                                                                                   ##STR39##                                                                            "    "                               218                                                                                 ##STR40##     NHCOCH.sub.3                                                                          OCH.sub.3                                                                          "       H    navy blue                       219                                                                                 ##STR41##     "       OC.sub.2 H.sub.5                                                                   "       "    "                               220                                                                                 ##STR42##     CH.sub.3                                                                              H    "       C.sub.2 H.sub.5                                                                    scarlet red                     __________________________________________________________________________

                                      TABLE 10                                    __________________________________________________________________________    Example No.                                            Nuance on              __________________________________________________________________________                                                           PES                    221                                                                                    ##STR43##                                     navy blue              222                                                                                    ##STR44##                                     navy blue              223                                                                                    ##STR45##                                     navy blue              224                                                                                    ##STR46##                                     navy blue              225                                                                                    ##STR47##                                     yellow brown           226                                                                                    ##STR48##                                     yellow brown           227                                                                                    ##STR49##                                     yellow                 228                                                                                    ##STR50##                                     navy blue              229                                                                                    ##STR51##                                     blue                   230                                                                                    ##STR52##                                     blue                   231                                                                                    ##STR53##                                     blue                   232                                                                                    ##STR54##                                     navy blue              233                                                                                    ##STR55##                                     blue                   234                                                                                    ##STR56##                                     blue                   235                                                                                    ##STR57##                                     blue                   236                                                                                    ##STR58##                                     navy blue              237                                                                                    ##STR59##                                     greenish blue          238                                                                                    ##STR60##                                     blue                   239                                                                                    ##STR61##                                     blue                   240                                                                                    ##STR62##                                     navy blue              241                                                                                    ##STR63##                                     greenish blue          242                                                                                    ##STR64##                                     blue                   __________________________________________________________________________

Compounds of the formula ##STR65## in which the symbols are defined inTable 11 can be prepared from known compounds by an appropriate methodof Example 1 to 12.

                                      TABLE 11                                    __________________________________________________________________________    Ex. No.                                                                             R.sub.6                                                                           R.sub.7                                                                            R.sub.1    R.sub.2                                                                            R.sub.3    Z            Nuance on              __________________________________________________________________________                                                           PES                    243   CN  H    H          H    CH.sub.3   CH.sub.2 CHCH                                                                              ruby red               244   "   H    H          H    "          CH.sub.2 CHCHCl                                                                            "                      245   "   H    H          H    "          CH.sub.2 CCH "                      246   "   H    H          H    "          CH.sub.2 CH.sub.2 Br                                                                       "                      247   "   H    H          H    "          CH.sub.2 CH.sub.2 Cl                                                                       "                      248   "   H    H          H    "                                                                                         ##STR66##   "                      249   "   H    H          H    "                                                                                         ##STR67##   "                      250   "   H    H          H    n-C.sub.4 H.sub.9                                                                        C.sub.6 H.sub.5                                                                            "                      251   CN  H    H          H    CH.sub.3                                                                                  ##STR68##   ruby red               252   "   H    H          H    C.sub.2 H.sub.5                                                                          "            "                      253   "   H    H          H    CH.sub.3                                                                                  ##STR69##   "                      254   "   H    H          H    "                                                                                         ##STR70##   "                      255   "   H    H          H    "                                                                                         ##STR71##   "                      256   "   H    H          H    "                                                                                         ##STR72##   "                      257   "   H    H          H    CH.sub.3                                                                                  ##STR73##   ruby red               258   "   H    H          H    "                                                                                         ##STR74##   "                      259   "   H    H          H    "                                                                                         ##STR75##   "                      260   "   H    H          H    "                                                                                         ##STR76##   "                      261   NO.sub.2                                                                          Cl   NHCOCH.sub.3                                                                             OCH.sub.3                                                                          H          CH.sub.2 CHCH.sub.2                                                                        navy blue              262   "   Cl   "          "    CH.sub.2 CHCH.sub.2                                                                      "            "                      263   "   Br   "          OC.sub.2 H.sub.5                                                                   "          CH.sub.2 CHCHCl                                                                            "                      264   "   Cl   "          "    H          "            "                      265   "   Cl   "          OCH.sub.3                                                                          H          CH.sub.2 CHCH                                                                              "                      266   "   Br   "          "    CH.sub.2 CHCHCl                                                                          "            "                      267   "   Cl   NHCOC.sub.2 H.sub.5                                                                      "    H          CH.sub.2 CH.sub.2 Cl                                                                       "                      268   "   Cl   NHCOCH.sub.3                                                                             "    CH.sub.2 CHCH.sub.2                                                                      "            "                      269   "   Cl   NHCOCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                   CH.sub.2 CHCH.sub.2                                                                      "            navy blue              270   "   Cl   "          OCH.sub.3                                                                          H          "            "                      271   NO.sub.2                                                                          Cl    NHCOCH.sub.3                                                                            OC.sub.2 H.sub.5                                                                   H                                                                                         ##STR77##   "                      272   "   "    "          "    CH.sub.2 CCH                                                                             "            "                      273   "   "    "          "    H          "            "                      274   "   Br   "          OCH.sub.3                                                                          H          C.sub.6 H.sub.5                                                                            "                      275   "   Br   NHCOCHCH.sub.2                                                                           "    CH.sub.2 CHCH.sub.2                                                                      "            "                      276   "   Cl   "          "    H                                                                                         ##STR78##   "                      277   NO.sub.2                                                                          Cl   NHCOCH.sub.3                                                                             "    CH.sub.2 CHCH.sub.2                                                                       ##STR79##   "                      278   "   Cl   "          OC.sub.2 H.sub.5                                                                   H                                                                                         ##STR80##   "                      279   "   Cl   "          OCH.sub.3                                                                          CH.sub.2 CHCHCl                                                                          CH.sub.2 CH.sub.2 Cl                                                                       "                      280   "   Cl   "          "    CH.sub.2 CHCH.sub.2                                                                       ##STR81##   "                      281   Cl  Cl   H          H    CH.sub.3   CH.sub.2 CHCH.sub.2                                                                        yellow brown           282   Cl  Cl   H          H    "          CH.sub.2 CHCHCl                                                                            "                      283   Cl  Cl   H          H    "          CH.sub.2 CHCH                                                                              "                      284   Cl  Cl   H          H    "                                                                                         ##STR82##   "                      285   Cl  Cl   H          H    "                                                                                         ##STR83##   "                      286   Cl  Br   H          H    CH.sub.2 CH.sub.3                                                                        "            "                      287   Cl  Cl   H          H    CH.sub.3   C.sub.6 H.sub.5                                                                            yellow brown           288   Cl  Cl   H          H    CH.sub.2 CH.sub.3                                                                         ##STR84##   "                      289   Cl  Cl   H          H    CH.sub.2 CHCH.sub. 2                                                                      ##STR85##   "                      290   Cl  Cl   H          H    CH.sub.3                                                                                  ##STR86##   "                      291   Cl  Cl   H          H    "                                                                                         ##STR87##   "                      292   Cl  Cl   H          H    "                                                                                         ##STR88##   "                      293   Cl  Cl   H          H    "                                                                                         ##STR89##   "                      294   NO.sub.2                                                                          Br   NHCOCH.sub.3                                                                             H    CH.sub.2 CH.sub.3                                                                        "            violet                 295   "   Cl   "          H    "          CH.sub.2 CHCH.sub.2                                                                        "                      296   CN  CN   CH.sub.3   H    C.sub.3 H.sub.7                                                                          CH.sub.2 CHCH.sub.2                                                                        blue                   297   NO.sub.2                                                                          "    "          H    C.sub.4 H.sub.9                                                                           ##STR90##   "                      298   "   H    NHCOCHCH.sub.2                                                                           H    CH.sub.3   CH.sub.2 CHCH.sub.2                                                                        ruby                   __________________________________________________________________________                                                           red                

Compounds of the formula ##STR91## in which the symbols are defined inTable 12 can be prepared from known compounds by an appropriate methodof Example 1 to 12.

                                      TABLE 12                                    __________________________________________________________________________    Ex No                                                                              R.sub.6                                                                           R.sub.7                                                                          R.sub.1   R.sub.2                                                                             R.sub.3  R.sub.x                                                                           Nuance on PES                        __________________________________________________________________________    299  --CN                                                                              H  H         H     CH.sub.3 H   ruby red                             300  "   H  H         H     --CH.sub.2 CH.sub.3                                                                    H   "                                    301  "   H  H         H     --CH.sub.2 CH═CH.sub.2                                                             H   "                                    302  "   H  H         H     --CH.sub.3                                                                             4-NO.sub.2                                                                        "                                    303  --NO.sub.2                                                                        H  --NHCOCH.sub.3                                                                          H     --CH.sub.2 CH═CH.sub.2                                                             H   "                                    304  "   H  --NHCOC.sub.2 H.sub.5                                                                   H     --CH.sub.2 C.tbd.CH                                                                    H   "                                    305  "   H  --NHCOCH═CH.sub.2                                                                   H     --CH.sub.2 CH═CH.sub.2                                                             H   "                                    306  "   Cl --NHCOCH.sub.3                                                                          --OCH.sub.3                                                                         H        H   navy blue                            307  "   Br "         "     H        H   "                                    308  "   Cl "         OCH.sub.2 CH.sub.3                                                                  H        H   "                                    309  "   Cl "         --OCH.sub.3                                                                         --CH.sub.2 CH═CH.sub.2                                                             H   "                                    310  "   Cl "         "     --CH.sub.2 CH═CHCl                                                                 H   "                                    311  "   Cl --NHCOCH.sub.2 CH.sub.3                                                                 "     H        H   "                                    312  "   Cl --NHCO--OCH.sub.3                                                                       "     --CH.sub.2 CH═CH.sub.2                                                             H   "                                    313  "   Cl --NHCOCH.sub.3                                                                          "     H        4-NO.sub.2                                                                        "                                    314  "   Br "         "     --CH.sub.2 CH═CH.sub.2                                                             H   "                                    315  "   Br "         "     --CHC.tbd.CH                                                                           H   "                                    316  "   Cl "         "     "        H   "                                    317  Cl  Cl H         H     --CH.sub.3                                                                             H   yellow brown                         318  Cl  Cl H         H     "        4-NO.sub.2                                                                        "                                    __________________________________________________________________________

Compounds of the formula ##STR92## in which the symbols are defined inTable 13 can be prepared from known compounds by an appropriate methodof Example 1 to 12.

                                      TABLE 13                                    __________________________________________________________________________                                     Nuance                                       Ex. No.                                                                            R.sub.6                                                                           R.sub.7                                                                          R.sub.3      R.sub.4                                                                           R.sub.5                                                                           Polyester                                    __________________________________________________________________________    319  Cl  Cl --CH.sub.3   H   --CH.sub.3                                                                        yellow brown                                 320  Cl  Cl --CH.sub.3   --CH.sub.3                                                                        H   "                                            321  Br  Br --CH.sub.3   H   H   "                                            322  --CN                                                                              H  --CH.sub.2 C.sub.6 H.sub.5                                                                 H   H   ruby red                                     323  "   H  --CH.sub.2 CH.sub.2 --C.sub.6 H.sub.5                                                      H   H   "                                            324  "   H  --CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                                       H   H   "                                            325  "   H  --CH.sub.2 CH.sub.2 O--CO--OCH.sub.3                                                       H   H   bluish red                                   326  "   H  --CH.sub.2 CH═CH.sub.2                                                                 H   H   ruby red                                     327  Cl  Cl --CH.sub.2 CH.sub.3                                                                        H   H   yellow brown                                 328  --CN                                                                              H  --CH.sub.2 C.tbd.CH                                                                        H   H   ruby red                                     329  "   H  --CH.sub.3   H   --CH.sub.3                                                                        "                                            330  "   H  --CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5                                                    H   H   "                                            331  Br  Cl --CH.sub.3   H   H   yellow brown                                 __________________________________________________________________________

Compounds of the formula ##STR93## in which the symbols are defined inTable 14 can be prepared from known compounds by an appropriate methodof Example 1 to 12.

                                      TABLE 14                                    __________________________________________________________________________    Ex. No.                                                                            DK                  R.sub.1 R.sub.2                                                                          R.sub.3    Nuance on                      __________________________________________________________________________                                                   PES                            332                                                                                 ##STR94##          H       H  C.sub.2 H.sub.5                                                                          ruby                           333                                                                                 ##STR95##          H       H  C.sub.4 H.sub.9                                                                          "                              334  "                   H       H  CH.sub.2 CH.sub.2 CN                                                                     red                            335                                                                                 ##STR96##          H       H  CH.sub.3   "                              336                                                                                 ##STR97##          H       H  C.sub.2 H.sub.4 CN                                                                       scarlet                        337                                                                                 ##STR98##          H       H  "          "                              338                                                                                 ##STR99##          NHCOCH.sub.3                                                                          H  "          red                            339  "                   "        Cl                                                                              H          scarlet                        340                                                                                 ##STR100##         "       "  H          ruby                           341                                                                                 ##STR101##         H       H  CH.sub.3   "                              342                                                                                 ##STR102##         H       H  CH.sub.2 CHCH.sub.2                                                                      yellow brown                   343                                                                                 ##STR103##         H       H  C.sub.4 H.sub.9                                                                          "                              344                                                                                 ##STR104##         H       H  CH.sub.2 CHCH.sub.2                                                                      "                              345                                                                                 ##STR105##         H       H  "          "                              346                                                                                 ##STR106##         NHCOCH.sub.3                                                                          C.sub.2 H.sub.5                                                                  bluish violet                             347                                                                                 ##STR107##         CH.sub.3                                                                              H  C.sub.4 H.sub.9                                                                          reddish blue                   348  "                   NHCOCH.sub.3                                                                          H  C.sub.3 H.sub.7                                                                          blue                           349  "                   NHCOC.sub.2 H.sub.5                                                                   H  "          "                              350  "                   NHCOCH.sub.3                                                                          H  C.sub.2 H.sub.5 /C.sub.3 H.sub.7                                              (1:1)      "                              351                                                                                 ##STR108##         CH.sub.3                                                                              H  C.sub.2 H.sub.5                                                                          scarlet                        352  "                   NHCOC.sub.2 H.sub.5                                                                   H  C.sub.2 H.sub.5                                                                          bluish red                     353  "                   NHSO.sub.2 CH.sub.3                                                                   H  C.sub.2 H.sub.5 /C.sub.3 H.sub.7                                              (1:1)      red                            354                                                                                 ##STR109##         NHCOC.sub.2 H.sub.5                                                                   H  "          ruby                           355                                                                                 ##STR110##         CH.sub.3                                                                              H  C.sub.4 H.sub.9                                                                          bluish violet                  356                                                                                 ##STR111##         H       H  CH.sub.3   bluish red                     357  "                   CH.sub.3                                                                              H  C.sub.2 H.sub.5                                                                          violet                         358  "                   NHCOCH.sub.3                                                                          H  C.sub.2 H.sub.4 CN                                                                       bluish red                     359                                                                                 ##STR112##         CH.sub.3                                                                              H  C.sub.2 H.sub.5                                                                          scarlet                        360  "                   NHCOC.sub.2 H.sub.5                                                                   H  "          red                            361                                                                                 ##STR113##         H       H  C.sub.2 H.sub.5                                                                          scarlet                        362  "                   CH.sub.3                                                                              H  "          red                            363  "                   NHCOCH.sub.3                                                                          H  "          ruby                           364  "                   "       H  C.sub.2 H.sub.4 CN                                                                       red                            365                                                                                 ##STR114##         CH.sub.3                                                                              H  C.sub.4 H.sub.9                                                                          bluish red                     366                                                                                 ##STR115##         "       H  C.sub.2 H.sub.5                                                                          dark blue                      367  "                   NHCOCH.sub.3                                                                          H  C.sub.2 H.sub.5 /C.sub.3 H.sub.7                                              (1:1)      greenish blue                  368                                                                                 ##STR116##         H       H  C.sub.2 H.sub.5                                                                          blue                           369  "                   CH.sub.3                                                                              H  "          greenish blue                  370  "                   H       H  C.sub.2 H.sub.4 OCOCH.sub.3                                                              reddish blue                   371  "                   NHCOCH.sub.3                                                                          H  C.sub.2 H.sub.5                                                                          bluish green                   372                                                                                 ##STR117##         CH.sub.3                                                                              H  C.sub.4 H.sub.9                                                                          reddish blue                   373                                                                                 ##STR118##         "       H  C.sub.2 H.sub.5                                                                          reddish navy                   374                                                                                 ##STR119##         H       H  "          dark blue                      375                                                                                 ##STR120##         H       H  "          "                              376                                                                                 ##STR121##         H       H  C.sub.2 H.sub.5                                                                          greenish blue                  377                                                                                 ##STR122##         NHCOCH.sub.3                                                                          H  CH.sub.2 CCH                                                                             red                            378  "                   "       H  "          bluish red                     379                                                                                 ##STR123##         H       H  C.sub.2 H.sub.5                                                                          violet                         380                                                                                 ##STR124##         H       H  C.sub.2 H.sub.4 CN                                                                       violet                         381                                                                                 ##STR125##         CH.sub.3                                                                              H  C.sub.2 H.sub.5                                                                          "                              382  "                   "       H  CH.sub.3   "                              383                                                                                 ##STR126##         CH.sub.3                                                                              H  "          ruby                           384  "                   H       H  C.sub.2 H.sub.5                                                                          red                            385                                                                                 ##STR127##         NHCOC.sub.2 H.sub.5                                                                   H  "          blue                           386                                                                                 ##STR128##         NHCOCH.sub.3                                                                          H  "          "                              387  "                   "       H  C.sub.2 H.sub.5 /C.sub.3 H.sub.7                                              (1:1)      "                              388                                                                                 ##STR129##         "       H  "          bluish violet                  389                                                                                 ##STR130##         NHCOCH.sub.3                                                                          H  C.sub.2 H.sub.5                                                                          "                              390                                                                                 ##STR131##         "       H  "          red                            __________________________________________________________________________

Compounds of the formula ##STR132## in which the symbols are defined inTable 15 can be prepared from known compounds by an appropriate methodof Example 1 to 12.

                                      TABLE 15                                    __________________________________________________________________________    Ex. No.                                                                            M R.sub.7                                                                           R.sub.8                                                                              R.sub.3    Nuance on PES                                    __________________________________________________________________________    391  H --Br                                                                              --CH.sub.3                                                                           H          navy blue                                        392  H "   --C.sub.2 H.sub.5                                                                    H          "                                                393  H "   --C.sub.2 H.sub.4 OCH.sub.3                                                          H          "                                                394  H Cl  --CH.sub.3                                                                           H          "                                                395  Cl                                                                              "   "      H          "                                                396  H "   --C.sub.2 H.sub.4 OCH.sub.3                                                          H          "                                                397  H "   --C.sub.2 H.sub.5                                                                    H          "                                                398  H "   --CH.sub.3                                                                           --C.sub.2 H.sub.5                                                                        greenish navy blue                               399  H "   "      --CH.sub.2 --CH═CH.sub.2                                                             navy blue                                        400  H Br  "      --CH.sub.2 --CH═CHCl                                                                 reddish navy blue                                401  H Cl  "      --CH.sub.2 --CH═CH.sub.2                                                             "                                                402  H "   "      --CH.sub.2 --C.sub.6 H.sub.5                                                             navy blue                                        403  H "   --C.sub.2 H.sub.5                                                                    --CH.sub.2 --CH═CH.sub.2                                                             "                                                404  H "   "      --CH.sub.2 --CH═CH--Cl                                                               "                                                405  H "   "      --CH.sub.3 --C.tbd.CH                                                                    reddish navy blue                                406  H Cl  --CH.sub.3                                                                           --C.sub.2 H.sub.4 --C.sub.6 H.sub.5                                                      greenish navy blue                               407  H "   "      --C.sub.3 H.sub.6 O--C.sub.6 H.sub.5                                                     "                                                408  H H   "      --CH--CH═CH--Cl                                                                      reddish navy blue                                409  H --I "      --CH.sub.2 CH═CH.sub.2                                                               "                                                410  H --CN                                                                              "      "          greenish blue                                    411  H "   "      --C.sub.2 H.sub.5                                                                        bluish green                                     __________________________________________________________________________

Compounds of the formula ##STR133## in which the symbols are defined inTable 16 can be prepared from known compounds by an appropriate methodof Example 1 to 12.

                                      TABLE 16                                    __________________________________________________________________________                                                     Nuance on                    Ex. No.                                                                            R.sub.40  Z     R.sub.1                                                                              R.sub.2  R.sub.3     PES                          __________________________________________________________________________    412  O         CCN   CH.sub.3                                                                             H        C.sub.2 H.sub.5                                                                           blue                         413  O         "     "      H        C.sub.4 H.sub.9                                                                           "                            414                                                                                 ##STR134##                                                                             "     "      H        C.sub.2 H.sub.5                                                                           greenish- blue               415                                                                                 ##STR135##                                                                             "     "      H        "           "                            416  O         "     NHCOCH.sub.3                                                                         H        "           red blue                     417  O         N     CH.sub.3                                                                             H        "           violet                       418  O         "     NHCOCH.sub.3                                                                         OCH.sub.3                                                                              H           navy blue                    419  O         "     "      "        CH.sub.2 CHCH.sub.2                                                                       "                            420  O         "     "      "        CH.sub.2 CHCHCl                                                                           "                            421  O         "     "      OC.sub.2 H.sub.5                                                                       "           "                            422  O         "     "      "        CH.sub.2 CHCH.sub.2                                                                       "                            423  O         "     "      OC.sub.2 H.sub.4 COCH.sub.3                                                            "           "                            424  O         "     "      OC.sub.2 H.sub.5                                                                       "           "                            425  O.sub.2 NCH                                                                             "     CH.sub.3                                                                             H        C.sub.2 H.sub.5                                                                           blue                         426                                                                                 ##STR136##                                                                             "     "      H        "           "                            __________________________________________________________________________

Compounds of the formula ##STR137## in which the symbols are defined inTable 17 can be prepared from known compounds by an appropriate methodof Example 1 to 12.

    __________________________________________________________________________                                                 Nuance on                        Ex. No.                                                                            DK             R.sub.1                                                                              R.sub.2                                                                            Y       R.sub.3                                                                            PES                              __________________________________________________________________________    427                                                                                 ##STR138##    H      H    CH.sub.2 CH.sub.2 CH.sub.2                                                            CH.sub.3                                                                           ruby                             428  "              H      H                                                                                   ##STR139##                                                                           "    "                                429                                                                                 ##STR140##    NHCOCH.sub.3                                                                         OCH.sub.3                                                                          "       H    marine blue                      430                                                                                 ##STR141##    "      OC.sub.2 H.sub.5                                                                   "       H    "                                431                                                                                 ##STR142##    CH.sub.3                                                                             H    "       C.sub.2 H.sub.5                                                                    scarlet red                      __________________________________________________________________________

EXAMPLE 432-433

The following compounds can be prepared analogously to an appropriatemethod of Examples 1 to 12. ##STR143##

EXAMPLE 434

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred into 100 parts of93% cold sulphuric acid and are then reacted, over 30 minutes with 32parts of 40% nitrosylsulphuric acid at 0°-5° C.

The resultant diazonium solution is stirred for 3 to 4 hours at 0°-5° C.and is then poured onto a mixture of 26.1 parts of3-(N-methyl-N-phenylamino)propionic acid-2'-trifluoroethyl ester, 100parts of glacial acetic acid, 2 parts of amidosulphonic acid, 200 partsof water and 500 parts of ice.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The purification,the dyestuff canbe recrystallized or column chromatographed. The resulting dyestuff isof the formula 434a ##STR144##

This dyestuff can dye polyester material a ruby red colour and hasexcellent fastness properties, especially good wet fastness propertiesafter thermofixation at 180° C. This dyestuff is particularly suited formodern Rapid Dyeing processes.

    λmax=538 nm (DMF).

EXAMPLE 435

21.8 parts of 2-chloro-4,6-di-nitroaniline are stirred into 150 parts of93% sulphuric acid at 15°-20° C. and are then reacted, over 30 minuteswith 32 parts of 40% nitrosylsulphuric acid.

This is stirred for 2 to 3 hours and the resultant diazonium solution ispoured over 15-20 minutes, onto a mixture of 41 parts of3-(N-3'"-chloroallyl-N-5"-acetylamino-2"-methoxyphenylamino)propionicacid-2'-trifluoroethyl ester, 100 parts of glacial acetic acid, 2 partsof amidosulphonic acid and 300 parts of ice. To complete the coupling,sodium acetate is added.

The resultant precipitated dyestuff is filtered, washed salt free withwater and dried under vacuum at 60° C. The resulting dyestuff is thenrecrystallised or column chromatographed to purify the product. Theproduct is a compound of the formula 435a ##STR145##

This dyestuff can dye polyester material a navy blue colour and hasexcellent fastness properties, especially good wet fastness properties.This dyestuff is particularly suited for modern Rapid Dyeing processes.The λmax=595 nm (DMF).

EXAMPLE 436

18.7 parts of 2-amino-4-chloro-3-cyano-5-formyl-thiophene are dissolvedin 200 parts of 85% phosphoric acid at -10° to -5° C. Whilst stirring,33.3 parts of 40% nitrosyl sulphuric acid are added and the mixturestirred for about 3-4 hours at about 0° C. The resulting solution isadded whilst stirring well, to a solution of 27.5 parts of3-(N-ethyl-N-3"-methylphenylamino)-propionic acid-2'-trifluoroethylester, 250 parts of glacial acetic acid, 80 parts water and 1000 partsof ice. The mixture is stirred for 30 minutes and then diluted slowlywith 2000 parts of icewater. The dyestuff suspension is filtered andwashed acid free with water. The product is dried under vacuum at 50° C.

The resulting dyestuff is then recrystallised or column chromatographedto purify the product. A dyestuff of the formula 436a ##STR146##results.

This dyestuff dyes polyester fibres a clear reddish blue tone with goodfastness properties, especially good wet fastness properties (ie in theC4A wash test from M&S) after thermofixing at 180° C. The product isparticularly suitable for Rapid Dyeing processes.

EXAMPLES 437-503

In Table 18, compounds of the formula ##STR147## where the symbols areas defined in Table 18 as well as the dyes of Tables 19-21 can be madeanalogously to Examples 434-436 from appropriate reactants.

                                      TABLE 18                                    __________________________________________________________________________    Ex. No.                                                                            DK                     R.sub.1  R.sub.2                                                                           R.sub.3      Nuance on               __________________________________________________________________________                                                          PES                     437                                                                                 ##STR148##            H        H   CH.sub.2 C.sub.6 H.sub.5                                                                   ruby red                438  "                      H        H   C.sub.2 H.sub.5                                                                            "                       439  "                      H        H   C.sub.2 H.sub.4 CN                                                                         "                       440  "                      H        H   C.sub.2 H.sub.4 OCOCH.sub.3                                                                "                       441                                                                                 ##STR149##            H        H   CH.sub.3     "                       442                                                                                 ##STR150##            NHCOCH.sub.3                                                                           H   C.sub.2 H.sub.2 CN                                                                         red                     443  "                      "        Cl  H            scarlet                 444                                                                                 ##STR151##            "        "   H            ruby red                445                                                                                 ##STR152##            H        H   C.sub.2 H.sub.5                                                                            yellow brown            446                                                                                 ##STR153##            H        H   CH.sub.2 C.sub.6 H.sub.5                                                                   "                       447                                                                                 ##STR154##            H        H   CH.sub.2 CH.sub.2 CN                                                                       yellow brown            448                                                                                 ##STR155##            CH.sub.3 H   C.sub.4 H.sub.9 -n                                                                         reddish blue            449  "                      NHCOCH.sub.3                                                                           H   C.sub.3 H.sub.7 -n                                                                         blue                    450  "                      NHCOC.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.7 -n                                                                         "                       451                                                                                 ##STR156##            CH.sub.3 H   C.sub.2 H.sub.5                                                                            scarlet                 452  "                      NHCO.sub.2 C.sub.2 H.sub.5                                                             H   "            blue red                453                                                                                 ##STR157##            CH.sub.3 H   C.sub.4 H.sub.9 n                                                                          bluish violet           454                                                                                 ##STR158##            H        H   CH.sub.3     bluish red              455  "                      CH.sub.3 H   C.sub.2 H.sub.5                                                                            Violet                  456  "                      NHCOCH.sub.3                                                                           H   C.sub.2 H.sub.4 CN                                                                         bluish red              457                                                                                 ##STR159##            H        H   C.sub.2 H.sub.5                                                                            scarlet                 458  "                      CH.sub.3 H   "            red                     459                                                                                 ##STR160##            "        H   C.sub.2 H.sub.4 CN                                                                         red                     460                                                                                 ##STR161##            CH.sub.3 H   C.sub.4 H.sub.9 n                                                                          bluish red              461                                                                                 ##STR162##            "        H   C.sub.2 H.sub.5                                                                            dark blue               462  "                      NHCOCH.sub.3                                                                           H   C.sub.2 H.sub.5 /C.sub.3 H.sub.7                                              (1:1)        greenish blue           463                                                                                 ##STR163##            H        H   C.sub.2 H.sub.5                                                                            blue                    464  "                      CH.sub.3 H   "            greenish blue           465  "                      NHCOCH.sub.3                                                                           H   C.sub.2 H.sub.5                                                                            green                   466                                                                                 ##STR164##            CH.sub.3 H   C.sub.4 H.sub.9 n                                                                          reddish blue            467                                                                                 ##STR165##            H        H   "            dark blue               468                                                                                 ##STR166##            H        H   C.sub.2 H.sub.5                                                                            greenish navy           469                                                                                 ##STR167##            NHCOC.sub.2 H.sub.5                                                                    H   "            blue                    470  "                      NHCOCH.sub.3                                                                           H   "            blue                    471  "                      "        H   C.sub.2 H.sub.5 /C.sub.3 H.sub.7                                              -n (1:1)     "                       472                                                                                 ##STR168##            "        H   "            bluish violet           473  "                      NHCOC.sub.2 H.sub.5                                                                    H   "            "                       474                                                                                 ##STR169##            "        H   "            red                     __________________________________________________________________________

                                      TABLE 19                                    __________________________________________________________________________     ##STR170##                                                                   Ex. No.                                                                            M  R.sub.7                                                                          R.sub.8                                                                              R.sub.3         Nuance on PES                               __________________________________________________________________________    475  H  Br CH.sub.3                                                                             H               navy blue                                   476  H  "  C.sub.2 H.sub.5                                                                      H               "                                           477  H  Cl CH.sub.3                                                                             H               "                                           478  Cl Cl CH.sub.3                                                                             H               "                                           479  H  "  C.sub.2 H.sub.4 OCH.sub.3                                                            H               "                                           480  H  "  "      CH.sub.2 CHCH.sub.2                                                                           greenish navy                               481  H  Br "      CH.sub.2 CHCHCl reddish navy                                482  H  "  "      CH.sub.2 CCH    "                                           483  H  "   C.sub.2 H.sub.5                                                                     H               navy blue                                   484  H  "  "      CH.sub.2 CHCH.sub.2                                                                           greenish navy                               485  H  "  CH.sub.3                                                                             CH.sub.2 CHCHCl reddish navy                                486  H  CN "      "               greenish blue                               487  H  Cl "      CH.sub.2 COOCH.sub.2 CCH                                                                      reddish navy blue                           488  H  "  "      CH.sub.2 COOCH.sub.2 CHCH.sub.2                                                               "                                           489  H  "  "      CH.sub.2 COOC.sub.2 H.sub.5                                                                   "                                           __________________________________________________________________________

                                      TABLE 20                                    __________________________________________________________________________     ##STR171##                                                                   Ex. No.                                                                            R.sub.40    Z     R.sub.1                                                                              R.sub.2                                                                            R.sub.3     Nuance on                      __________________________________________________________________________                                                   PES                            490  O           CCN   CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                           bluish violet                  491  O           "     "      H    C.sub.4 H.sub.9 -n                                                                        "                              492  CHNO.sub.2  "     "      H    C.sub.2 H.sub.5                                                                           blue                           493  C(CN)COOC.sub.2 H.sub.5                                                                   "     "      H    "           "                                   C(CN)COOC.sub.4 H.sub.9 n                                                     (1:1 ratio)                                                              494  O           N     NHCOCH.sub.3                                                                         OCH.sub.3                                                                          H           navy blue                      495  O           N     "      "    CH.sub.2 CHCH.sub.2                                                                       reddish navy                   496  O           "     "      OCH.sub.3                                                                          CH.sub.2 CHCHCl                                                                           "                              497  O           "     "      OC.sub.2 H.sub.5                                                                   "           "                              498  O           "     "      "    CH.sub.2 CHCH.sub.2                                                                       "                              499  O           "     "      OC.sub.2 H.sub.5                                                                   "           "                              __________________________________________________________________________

                                      TABLE 20                                    __________________________________________________________________________    Ex. No.                          Nuance on PES                                __________________________________________________________________________    500                              blue                                          ##STR172##                                                                   501                              navy blue                                     ##STR173##                                                                   502                              blue                                          ##STR174##                                                                   503                              ruby red                                      ##STR175##                                                                   __________________________________________________________________________

EXAMPLE 504

17.4 parts of 1-amino-2,4-dinitro-6-chlorobenzene are dissolved in 137parts of 93% sulphuric acid. The mixture is cooled to 10° to 15° C.Whilst stirring well, 33.3 parts of 40% nitrosyl sulphuric acid areadded and the mixture stirred for about 1 hour at about 0° C. Theresulting solution is added over 15 minutes to a solution of 40 parts of3-(N-allyl-N-2"-methoxy-5"-acetylamino-phenylamino)propionicacid-2'-tetrafluoropropyl ester, 500 parts of water and 800 parts oficewater. To complete the reaction sodium acetate is added. The dyestuffsuspension is filtered and washed acid free with water. The product isdried under vacuum at 50° C. The resulting dyestuff is thenrecrystallised or column chromatographed to purify the product. Adyestuff of the formula 504a ##STR176## results.

This dyestuff dyes polyester fibres a navy blue tone with good fastnessproperties.

In the Examples where column chromatography is performed the eluent isethylmethylketone/toluene.

Application Example

The dyestuff of Example 1 (of formula 1a) is sandmilled with acommercially available dispersing agent, for example a commerciallyavailable lignin sulphonate and then the mixture is sprayed dry to anultrafine powder having an average particle size of 1μ and a coupageratio of 3.5:10.

12 parts of this ultra fine powder are dispersed in 100 parts of waterand this is added at 60° C. to 13,000 parts of a circulating liquor(containing 30 parts of ammonium sulphate and 0.3 parts of formic acidas a buffer and optionally a carrier-/levelling agent combination).

In a dyeing autoclave with a precleaned pressed cross spool of 1000parts of polyester yarn on a plastic holder the circulating liquor isthen heated to 130° C. over 35 minutes. After 90 minutes at 130° C., theautoclave is cooled to 80° C. and the exhausted liquor is drained off.The resulting dyed substrate is washed thoroughly with cold water andthen reductively cleared according to known art standard methods andfinally dried. A level, deep ruby red colour results.

The Application Example can be repeated using, instead of the dyestuffof Example 1, an appropriate amount of any one of Examples 2 to 504.

What is claimed is:
 1. A compound of the formula I ##STR177## in which Dis a diazo component;K is an aromatic group of the formula a, b or c##STR178## where R is a group of the formula --CH(R₄)--CO--O--R₅, --CH₂CF₃ or --CH₂ CF₂ CF₂ H; R₆ is hydrogen or hydroxy, R₁ is hydrogen,chloro, C₁₋₄ alkyl, C₁₋₄ alkoxy or acylamino, R₂ is hydrogen, C₁₋₄alkoxy, C₁₋₄ alkoxyethoxy, chloro, bromo and R₃ is selected fromhydrogen, C₁₋₆ alkyl, C₃₋₄ alkenyl, chloroC₃₋₄ alkenyl, bromoC₃₋₄alkenyl, C₃₋₄ alkynyl, phenyl-C₁₋₄ alkyl, C₁₋₄ alkoxycarbonyl-C₁₋₄alkyl, C₃₋₄ alkenyloxycarbonyl-C₁₋₄ alkyl, C₃₋₄ alkynyloxycarbonyl-C₁₋₄alkyl, phenoxy-C₂₋₄ alkyl, --CH₂ --CH(R₈)CH₂ --R₉ and C₂₋₄ alkylsubstituted by 1 to 3 groups selected from halogen, cyano, C₁₋₄ alkoxy,C₁₋₄ alkylcarbonyloxy and C₁₋₄ alkoxycarbonyloxy; or R₂ together with R₃in the group a) form a group of the formula-*CH(CH₃)CH₂ C(CH₃)₂ wherethe * carbon atom is attached to the group a); R₄ is hydrogen, phenyl orC₁₋₄ alkyl, R₅ is phenyl, unsubstituted or substituted by one to threegroups selected from halogen, C₁₋₄ alkyl, C₁₋₄ alkoxycarbonyl and C₁₋₄alkoxy or phenyl substituted by one group selected from formyl, cyan,rhodan, phenyl, benzyloxy, C₁₋₄ alkoxycarbonyl-C₁₋₂ alkoxy, C₁₋₄alkylcarbonylamino, C₁₋₄ alkylcarbonyloxy and nitro; alpha or betanaphthyl, phenyl-C₁₋₄ alkyl or 1-phenyl-propenyl-3, in which the phenylgroup (in phenyl C₁₋₄ alkyl and 1-phenyl propenyl-3) is unsubstituted orsubstituted by one or two substituents selected from halogen, C₁₋₄ alkyland C₁₋₄ alkoxy or by one nitro or C₁₋₄ alkoxycarbonyl group; or R₅ isallyl, haloallyl, methallyl, propargyl, tetrahydrofuryl-2-methyl,tetrahydropyranyl-2-methyl, chlor-C₂₋₄ alkyl, bromoC₂₋₄ alkyl or a groupof the formula ##STR179## R₇ is hydrogen or C₁₋₄ alkyl; R₈ is hydroxy,C₁₋₄ alkylcarbonyloxy or C₁₋₄ alkoxycarbonyloxy; R₉ is chloro, C₁₋₄alkoxy, phenoxy, allyloxy or C₁₋₄ alkylcarbonyloxy; R₁₀ is hydrogen orC₁₋₄ alkyl; R₁₁ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy or nitro Yis C₂₋₃ alkylene and n is 0 or 1;with the proviso that when K is a groupof formula b) or c), then R₃ is hydrogen (and mixtures containingcompounds of formula I).
 2. A compound according to claim 1 in which Dis a diazo component of the phenyl, thienyl, thiazolyl, isothiazolyl,thiadiazolyl, pyrazolyl, imidazolyl, triazolyl, benzthiazolyl, orbenzisothiazolyl series.
 3. A compound according to claim 1 in which Dis D₁ where D₁ is a compound of formula 1 to 11 below ##STR180## inwhich R₂₀ is hydrogen, chloro, bromo, cyano, nitro-, C₁₋₄ alkoxycarbonyl, C₁₋₄ alkylsulphonyl;R₂₁ is chloro, bromo, nitro, C₁₋₄ alkyl,C₁₋₄ alkylsulfonyl, C₁₋₄ alkylcarbonyl, aminosulfonyl, mono- or di-C₁₋₄alkylaminosulfonyl, phenylaminosulfonyl, C₁₋₄ alkoxycarbonyl,aminocarbonyl, mono- or di-C₁₋₄ -alkylaminocarbonyl,phenylaminocarbonyl, phenylazo, benzyloxycarbonyl,tetrahydro-furfuryl-2-oxycarbonyl, C₃₋₄ alkenyloxycarbonyl or C₃₋₄alkinyloxycarbonyl; R₂₂ is hydrogen, chloro, bromo or cyano; R₂₃ ishydrogen or chloro, or when R₂₂ is hydrogen, R₂₃ is additionally rhodan;R₂₄ is nitro, C₁₋₄ alkylcarbonyl, C₁₋₄ alkoxycarbonyl, cyano,aminocarbonyl, mono- or di-C₁₋₂ alkylaminocarbonyl; R₂₅ is hydrogenchloro, bromo, C₁₋₄ alkyl or phenyl; R₂₆ is nitro, cyano, formyl,dicyanovinyl or a group of the formula --CH═CH--NO₂, --CH═C(CN)CO--OC₁₋₄-alkyl, H₅ C₆ --N═N-- or 3- or 4--NO₂ --C₆ H₄ --N═N--; R₂₇ is cyano orC₁₋₄ alkoxycarbonyl; R₂₈ is C₁₋₄ alkyl or phenyl; R₂₉ is --CN, --CH═CH₂or phenyl; R₃₀ is C₁₋₄ alkyl; R₃₁ is hydrogen, chloro, bromo, cyano,rhodan, nitro, C₁₋₄ alkoxycarbonyl or di-C₁₋₄ alkylaminosulfonyl; R₃₂ ishydrogen chloro or bromo; and R₃₃ is C₁₋₄ alkyl, C₁₋₄alkoxycarbonyl-C₁₋₄ alkylene or --C₁₋₄ alkylene-COOCH₂ CF₃ in which anyphenyl group present in R₂₀ to R₃₀ is unsubstituted or substituted byone or two groups selected from chloro, bromo, methyl, ethyl, methoxyand ethoxy.
 4. A compound according to claim 1 in which K is K₁ where K₁is a group of formula a) defined above.
 5. A compound according to claim1 in which R is R' where R' is --CH(R₄ ')--CO--O--R₅ ' or --CH₂ CF₃where R₄ ' is selected from hydrogen and C₁₋₂ alkyl and R₅ ' is phenyl,unsubstituted or substituted by one or two substituents selected fromchloro, C₁₋₂ alkyl, C₁₋₂ alkoxy and one phenyl; phenyl C₁₋₂ alkyl,phenoxy ethyl or 1-phenylpropenyl-3, the phenyl group of each of thelast three substituents (phenyl C₁₋₂ alkyl, phenoxy ethyl or1-phenylpropenyl-3) being unsubstituted or substituted by one or twogroups selected from chloro, methyl and C₁₋₂ alkoxy or one group nitro)or R₅ ' is alpha and beta naphthyl.
 6. A compound according to claim 1in which R₁ is R₁ ' where R₁ ' is selected from hydrogen, C₁₋₂ alkyl,chloro and acylamino.
 7. A compound according to claim 1 in which R₂ isR₂ ' where R₂ ' is selected from hydrogen, chloro, C₁₋₂ alkoxy, C₁₋₂alkoxyethoxy or R₂ ' (when in formula a) together with R₃ forms thegroup --CH(CH₃)CH₂ C(CH₃)₂.
 8. A compound according to claim 1 in whichR₃ is R₃ ' where R₃ ' is selected from hydrogen, C₁₋₄ alkyl, cyanoethyl,C₁₋₂ alkoxyethyl, C₃₋₄ alkenyl, chloroallyl, C₃₋₄ alkynyl, C₁₋₂alkoxycarbonylmethyl, allyloxycarbonylmethyl orpropargyloxycarbonylmethyl.
 9. A compound according to claim 1 in whichR₄ is R₄ ' where R₄ ' is selected from hydrogen and C₁₋₂ alkyl.
 10. Acompound according to claim 1 in which R₅ is R₅ ' where R₅ ' is phenyl,unsubstituted or substituted by one or two substituents selected fromchloro, C₁₋₂ alkyl, C₁₋₂ alkoxy and one phenyl; phenyl C₁₋₂ alkyl,phenoxy ethyl or 1-phenylpropenyl-3, the phenyl group of each of thelast three substituents (phenyl C₁₋₂ alkyl, phenoxy ethyl or1-phenylpropenyl-3) being unsubstituted or substituted by one or twogroups selected from chloro, methyl and C₁₋₂ alkoxy or one group nitro)or R₅ ' is alpha and beta naphthyl.
 11. A compound according to claim 1in which Y is Y' where Y' is a group of the formula

    --CH.sub.2 CH.sub.2 -- or --CH.sub.2 CH(CH.sub.3)--.


12. A compound according to claim 1 in which D is D₂ where D₂ is a diazocomponent of the2,6-dicyano-4-chlorophenyl,2,6-dicyano-4-bromo-phenyl,2,6-dicyano-4-methylphenyl,2,6-dicyano-4-nitrophenyl 2,4-dinitro-6-chlorophenyl,2,4-dinitro-6-bromophenyl, 2,4-dinitro-6-cyanophenyl, 2-chloro- or2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dichloro- or2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro- or2-cyano-4-nitro-phenyl, 2,4-dinitro-5-chlorophenyl,2,4-dinitro-5,6-dichlorophenyl, 2,5-dichloro-4-nitro-phenyl,4-nitrophenyl, 4-phenylazophenyl, 4-C₁₋₄ alkoxy-carbonylphenyl, 2-C₁₋₄alkoxycarbonyl-4-nitrophenyl, 4-benzyloxycarbonylphenyl,4-(tetrahydro-furfuryl-2'-oxycarbonyl)-phenyl,3,5-dicyano-4-chlorothienyl-2,3,5-dicyanothienyl-2,3-cyano-5-nitro-thienyl-2,3-acetyl-5-nitro-thienyl-2,3,5-dinitrothienyl-2,3-(C₁₋₄alkoxycarbonyl)-5-nitro-thienyl-₂,5-phenylazo-3-cyano-thienyl-2,5-phenylazo-3-cyano-4-methyl-thienyl-2,5-nitro-thiazolyl-2,5-nitrobenziso-thiazolyl-3,3-methyl-4-cyano-isothiazolyl-5,3-Phenyl-1,2,4-thiadiazolyl-2,5-(C₁₋₂alkylmercapto)-1,3,4-thiadiazolyl-2,3-C₁₋₄alkoxycarbonylethylmercapto-1,2,4-thiadiazolyl-5,1-cyano-methyl-4,5-dicyano-imidazolyl-2,6-nitrobenzthiazolyl-2,5-nitrobenzthiazolyl-2,6-rhodanbenzthiazolyl-2,6-chlorobenzthiazolyl-2,(5),6,(7)-dichlorobenzthiazolyl-2,or a group of the formula ##STR181## where R₃₅ is oxygen or a group ofthe formula ##STR182##
 13. A compound according to claim 1 in which thecompounds of formula I are of formula Ia ##STR183## in which D₁ is acompound of formula 1 to 11 below ##STR184## in which R₂₀ is hydrogen,chloro, bromo, cyano, nitro-, C₁₋₄ alkoxy carbonyl, C₁₋₄alkylsulphonyl;R₂₁ is chloro, bromo, nitro, C₁₋₄ alkyl, C₁₋₄alkylsulfonyl, C₁₋₄ alkylcarbonyl, aminosulfonyl, mono- or di-C₁₋₄alkylaminosulfonyl, phenylaminosulfonyl, C₁₋₄ alkoxycarbonyl,aminocarbonyl, mono- or di-C₁₋₄ -alkylaminocarbonyl,phenylaminocarbonyl, phenylazo, benzyloxycarbonyl,tetrahydro-furfuryl-2-oxycarbonyl, C₃₋₄ alkenyloxycarbonyl or C₃₋₄alkinyloxycarbonyl; R₂₂ is hydrogen, chloro, bromo or cyano; R₂₃ ishydrogen or chloro, or when R₂₂ is hydrogen, R₂₃ is additionally rhodan;R₂₄ is nitro, C₁₋₄ alkylcarbonyl, C₁₋₄ alkoxycarbonyl, cyano,aminocarbonyl, mono- or di-C₁₋₂ alkylaminocarbonyl; R₂₅ is hydrogen,chloro, bromo, C₁₋₄ alkyl or phenyl; R₂₆ is nitro, cyano, formyl,dicyanovinyl or a group of the formula --CH═CH--NO₂, --CH═C(CN)CO--OC₁₋₄-alkyl, H₅ C₆ --N═N-- or 3- or 4-NO₂ --C₆ H₄ --N═N--; R₂₇ is cyano orC₁₋₄ alkoxycarbonyl; R₂₈ is C₁₋₄ alkyl or phenyl; R₂₉ is --CN, --CH═CH₂or phenyl; R₃₀ is C₁₋₄ alkyl; R₃₁ is hydrogen, chloro, bromo, cyano,rhodan, nitro, C₁₋₄ alkoxycarbonyl or di-C₁₋₄ alkylaminosulfonyl; R₃₂ ishydrogen chloro or bromo; and R₃₃ is C₁₋₄ alkyl, C₁₋₄alkoxycarbonyl-C₁₋₄ alkylene or --C₁₋₄ alkylene-COOCH₂ CF₃ in which anyphenyl group present in R₂₀ to R₃₀ is unsubstituted or substituted byone or two groups selected from chloro, bromo, methyl, ethyl, methoxyand ethoxy; R₁ ' where R₁ ' is selected from hydrogen, C₁₋₂ alkyl,chloro and acylamino; R₂ ' where R₂ ' is selected from hydrogen, chloro,C₁₋₂ alkoxy, C₁₋₂ alkoxyethoxy or R₂ ' (when in formula a) together withR₃ forms the group --CH(CH₃)CH₂ C(CH₃)₂ ; Y' where Y' is a group of theformula --CH₂ CH₂ -- or --CH₂ CH(CH₃)--; R₄ ' where R₄ ' is selectedfrom hydrogen and C₁₋₂ alkyl; and R₃ and R₅ are as defined in claim 1.14. A compound according to claim 1 in which the compounds of formula Iare of formula Ib ##STR185## in which D₂ is is a diazo component of the2,6-dicyano-4-chlorophenyl, 2,6-dicyano-4-bromophenyl,2,6-dicyano-4-methylphenyl,2,6-dicyano-4-nitrophenyl,2,4-dinitro-6-chlorophenyl,2,4-dinitro-6-bromophenyl, 2,4-dinitro-6-cyanophenyl, 2-chloro- or2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dichloro- or2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro- or2-cyano-4-nitrophenyl,2,4-dinitro-5-chlorophenyl,2,4-dinitro-5,6-dichlorophenyl,2,5-dichloro-4-nitro-phenyl,4-nitrophenyl,4-phenylazophenyl, 4-C₁₋₄ alkoxy-carbonyl-phenyl, 2-C₁₋₄alkoxycarbonyl-4-nitrophenyl, 4-benzyloxycarbonylphenyl,4-(tetrahydro-furfuryl-2'-oxy-carbonyl)-phenyl,3,5-dicyano-4-chlorothienyl-2,3,5-dicyanothienyl-2,3-cyano-5-nitro-thienyl-2,3-acetyl-5-nitrothienyl-2,3,5-dinitrothienyl-2,3-(C₁₋₄alkoxycarbonyl)-5-nitro-thienyl-2,5-phenylazo-3-cyanothienyl-2,5-phenylazo-3-cyano-4-methyl-thienyl-2,5-nitro-thiazolyl-2,5-nitro-benzisothiazolyl-3,3-methyl-4-cyano-isothiazolyl-5,3-Phenyl-1,2,4-thiadiazolyl-2,5-(C₁₋₂alkylmercapto)-1,3,4-thiadiazolyl-2,3-C₁₋₄alkoxycarbonylethylmercapto-1,2,4-thiadiazolyl-5,1-cyanomethyl-4,5-dicyano-imidazolyl-2,6-nitrobenzthiazolyl-2,5-nitrobenzthiazolyl-2,6-rhodan-benzthiazolyl-2,6-chlorobenzthiazolyl-2,( 5),6,(7)-dichloro-benz-thiazolyl-2, or a group of the formula##STR186## where R₃₅ is oxygen or a group of the formula ##STR187## R₁ 'where R₁ ' is selected from hydrogen, C₁₋₂ alkyl, chloro andacylamino;R₂ ' where R₂ ' is selected from hydrogen, chloro, C₁₋₂alkoxy, C₁₋₂ alkoxyethoxy or R₂ ' (when in formula a) together with R₃forms the group --CH(CH₃)CH₂ C(CH₃)₂ ; Y' where Y' is a group of theformula --CH₂ CH₂ -- or --CH₂ CH(CH₃)--; R₄ ' where R₄ ' is selectedfrom hydrogen and C₁₋₂ alkyl; and R₃ and R₅ are as defined in claim 1.15. A compound according to claim 1 in which the compounds of formula Iare those of formula Ic ##STR188## in which D₃ is a diazo component ofthe 2,4-dinitro-6-chlorophenyl, 2,4-dinitro-6-bromophenyl,2,4-dinitro-6-cyanophenyl, 2,4-dinitro-5-chlorophenyl or2,4-dinitro-5-rhodanphenyl, 2,4-dinitro-5,6-dichlorophenyl series;R' is--CH(R₄ ')--CO--O--R₅ ' or CH₂ CF₃ where R₄ ' and R₅ ' are definedbelow; R₁ " is acylamino; R₂ " is C₁₋₂ alkoxy or C₁₋₂ alkoxyethoxy, R₃ 'is selected from hydrogen, C₁₋₄ alkyl, cyanoethyl, C₁₋₂ alkoxyethyl,C₃₋₄ alkenyl, chloroC₃₋₄ alkenyl, C₃₋₄ alkynyl, C₁₋₂alkoxycarbonylmethyl, allyloxycarbonylmethyl, orpropargyl-oxycarbonylmethyl; R₄ ' is selected from hydrogen and C₁₋₂alkyl; R₅ ' is phenyl, unsubstituted or substituted by one or twosubstituents selected from chloro, C₁₋₂ alkyl, C₁₋₂ alkoxy and phenyl;phenyl C₁₋₂ alkyl, phenoxy ethyl or 1-phenylpropenyl-3, (the phenylgroup of each of the last three substituents (phenyl C₁₋₂ alkyl, phenoxyethyl or 1-phenylpropenyl-3) being unsubstituted or substituted by oneor two groups selected from chloro, methyl and C₁₋₂ alkoxy or one groupnitro) or R₅ ' is alpha and beta naphthyl; and Y is Y' where Y' is agroup of the formula --CH₂ CH₂ -- or --CH₂ CH(CH₃)--.
 16. A compoundaccording to claim 15 in which the compounds of formula Ic are those inwhichD₃ is D₃ ' where D₃ ' is a diazo component of the2,4-dinitro-6-chlorophenyl or 2,4-dinitro-6-bromophenyl series; R₁ " is--NH--COC₁₋₂ alkyl; R₂ " is R₂ '" where R₂ '" is C₁₋₂ alkoxy; R₃ ' isR_(3a) where R_(3a) is hydrogen, allyl, chloroallyl or propargyl; R₅ 'is R₅ " where R₅ " is phenyl, phenoxyethyl or benzyl, in which thephenyl group of each substituent is unsubstituted or substituted by oneor two groups selected from chloro, methyl and C₁₋₂ alkoxy or one groupnitro; R' is R'" where R'" is a group of the formula --CH₂ CO--O--R₅ ",where R₅ " is defined above; and Y is Y" where Y" is 1,2 ethylene.
 17. Acompound according to claim 1 in which the compounds of formula I arethose of formula Id ##STR189## in which D₄ is a diazo component of the4-nitrophenyl, 2-chloro-4-nitrophenyl, 2,6-dichloro-4-nitrophenyl,2-chloro-4-nitro-6-bromophenyl or 2-cyano-4-nitrophenyl series; R_(1a)is hydrogen, methyl, acylamino or chloro;R_(b) is a group of the formula--CH(R₄ ')--CO--O--R₅ ', where R₄ ' is selected from hydrogen and C₁₋₂alkyl and R₅ ' is phenyl, unsubstituted or substituted by one or twosubstituents selected from chloro, C₁₋₂ alkyl, C₁₋₂ alkoxy and phenyl;phenyl C₁₋₂ alkyl or 1-phenylpropenyl-3 (the phenyl group of each of thelast two substituents (phenyl C₁₋₂ alkyl or 1-phenylpropenyl-3) beingunsubstituted or substituted by one or two groups selected from chloro,methyl and C₁₋₂ alkoxy or one group nitro or R₅ ' is alpha and betanaphthyl; R_(3b) is C₁₋₄ alkyl, cyano-C₁₋₄ alkyl, C₁₋₄ alkoxyethyl, --C₂H₄ --O--CO--C₁₋₄ alkyl, --C₂ H₄ --O--CO--OC₁₋₄ alkyl or benzyl; R₄ ' isselected from hydrogen and C₁₋₂ alkyl; R₅ ' is phenyl, unsubstituted orsubstituted by one or two substituents selected from chloro, C₁₋₂ alkyl,C₁₋₂ alkoxy and phenyl; phenyl C₁₋₂ alkyl, or 1-phenylpropenyl-3 (thephenyl group of each of the last two substituents (phenyl C₁₋₂ alkyl or1-phenylpropenyl-3) being unsubstituted or substituted by one or twogroups selected from chloro, methyl and C₁₋₂ alkoxy or one group nitroor R₅ ' is alpha and beta naphthyl; and Y' is a group of the formula--CH₂ CH₂ -- or --CH₂ CH(CH₃)--.
 18. A compound according to claim 17 inwhich the compounds of formula Id are those in which D₄ is D₅ where D₅is 2,6-dichloro-4-nitrophenyl or 2-cyano-4-nitrophenyl and R_(1a) ishydrogen, R_(3b) is C₁₋₄ alkyl, R₄ ' is hydrogen and Y' is --CH₂ CH₂ --.19. A process for dyeing a substrate comprising applying to thesubstrate a compound of claim
 1. 20. A process for preparing a compoundaccording to claim 1 comprising coupling one mole of a diazotized amineof formula II

    D--NH.sub.2                                                (II)

with one mole of a compound of formula III

    H--K--N(R.sub.3)--Y--CO--O--R                              (III)

where the symbols are as defined in claim 1.